KR101811015B1 - Manufacturing method of carbon blakcs containing macro/meso pore structures - Google Patents

Manufacturing method of carbon blakcs containing macro/meso pore structures Download PDF

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KR101811015B1
KR101811015B1 KR1020150142728A KR20150142728A KR101811015B1 KR 101811015 B1 KR101811015 B1 KR 101811015B1 KR 1020150142728 A KR1020150142728 A KR 1020150142728A KR 20150142728 A KR20150142728 A KR 20150142728A KR 101811015 B1 KR101811015 B1 KR 101811015B1
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acid
present
carbon
black
manufacturing
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KR20170043699A (en
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박수진
한예지
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인하대학교 산학협력단
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/14—Pore volume
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/16—Pore diameter

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  • Carbon And Carbon Compounds (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Nanotechnology (AREA)
  • Inorganic Chemistry (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

The present invention relates to a method for producing carbon nanomaterials using Kecheon black, which is one kind of carbon black expressing atmospheric / mesoporous pores, which can be used in various fields. (1) Ketjen blacks ; (2) acid-treating the mixture containing Ketjen Blacks by stirring in the step (1); And (3) washing and drying the acid-treated mixture.
According to the present invention, it is possible to produce a new carbon nanomaterial having a high atmospheric hole and a medium pore volume through acid treatment of Kecheon black.

Description

TECHNICAL FIELD [0001] The present invention relates to a method for manufacturing a carbon nanomaterial,

The present invention relates to a method for producing carbon nanomaterials using Kecheon black, which is one type of carbon black expressing atmospheric / mesoporous pores, which can be used in various fields. More particularly, The present invention relates to a method for producing a new carbon nanomaterial that exhibits increased mesopore volume.

Currently, carbon materials are used in various fields such as adsorption, supercapacitors, batteries, and composites. Carbon materials are inexpensive, hydrophobic, thermally and chemically stable compared to relatively different materials. And the possibility of changing the structural characteristics of the material itself according to various applications. Among them, Kecheon Black is an incomplete combustion product of natural gas or tar and has a particulate form composed of 95% or more amorphous carbonaceous material. Among the carbon materials, Kecheon black has attracted attention as a battery material because it has a specific surface area higher than that of activated carbon and an average pore size and an air / medium pore volume. In order to further reveal the above characteristics, it is necessary to increase the atmospheric air / medium pores of Kecheon black. There are various methods for changing the structural characteristics of the carbon material as follows.

In order to change the structural characteristics of the carbon material, there are acid treatment and physical / chemical activation methods. Physical / chemical activation method is usually used as a method to increase micro-pores and small mesopores or specific surface area. It is a way to change the pore.

Korean Patent Registration No. 10-0913998

It is an object of the present invention to provide a new carbon nanomaterial having an increased atmospheric hole and mesopore volume than the existing Kecheon black through acid treatment.

According to an aspect of the present invention, there is provided a method of manufacturing a semiconductor device, comprising: (1) supporting Ketjen blacks on an acid solution; (2) acid-treating the mixture containing Ketjen Blacks by stirring in the step (1); And (3) washing the acid-treated mixture and drying the carbon nanomaterial.

In the step (1), the acid solution may be prepared from the group consisting of 20 to 85% phosphoric acid (H 3 PO 4 ), 20 to 60% nitric acid (HNO 3 ) and 20 to 98% sulfuric acid (H 2 SO 4 ) And Ketjen Blacks may be 0.5 to 3 g per 100 mL of the acid solution.

The step (2) may be carried out at 25 to 80 ° C for 0.5 to 24 hours.

In the step (3), the acid-treated mixture may be washed to neutralize the pH, recovered with a reduced pressure filter, and dried at 25 to 100 ° C.

According to another aspect of the present invention, there is provided a carbon nanomaterial produced by the method of one aspect of the present invention.

According to the present invention, it is possible to produce a new carbon nanomaterial having a high atmospheric hole and a medium pore volume through acid treatment of Kecheon black.

Also, when the carbon nanomaterial according to the present invention is manufactured under various conditions, it is possible to control the volume of the air / medium pores.

1 is a nitrogen adsorption isotherm of a new carbon nanomaterial produced through an acid treatment obtained in the production method according to an embodiment of the present invention.
2 is a pore size distribution diagram of an activated new carbon nanomaterial obtained in the manufacturing method according to an embodiment of the present invention.

Hereinafter, the present invention will be described in detail.

A method of manufacturing an air / medium cavity carbon nanomaterial according to an embodiment of the present invention comprises the steps of: (1) supporting Ketjen blacks on an acid solution; (2) acid-treating the mixture containing Ketjen Blacks by stirring in the step (1); And (3) washing and drying the acid-treated mixture.

Step (1) is that by supporting the kecheon black in acid to a change in the pore characteristics, the type of the acid in the step of carrying the kecheon black in the step (1) in an acid solution is 20 to 85% phosphoric acid (H 3 PO 4 ), 20 to 60% of nitric acid (HNO 3 ) and 20 to 98% of sulfuric acid (H 2 SO 4 ), and the amount of Kecheon black is 0.5 to 3 g per 100 mL of the acid solution And preferably 1 to 2 g per 100 mL of the acid solution.

In the step (2), the mixture containing Ketone Black obtained in the step (1) may be stirred at 25 to 80 ° C and stirred for 0.5 to 24 hours. The stirring speed may be 100 to 500 rpm.

In the step (3), the mixture obtained in the step (2) may be washed with distilled water and / or ethanol so as to have a pH of 6.5 to 7.5, and then recovered with a reduced pressure filter and dried at 25 to 100 ° C for 24 hours. If the drying temperature is less than 25 ° C, the drying is difficult. If the drying temperature exceeds 100 ° C, the sample may be deformed.

The present invention provides a carbon nanomaterial in which atmospheric / mesoporous pores are produced by the above-described production method.

Hereinafter, the present invention will be described in more detail with reference to Examples. It is to be understood by those skilled in the art that these examples are for illustrative purposes only and that the scope of the present invention is not construed as being limited by these examples.

Example 1.

Acid treatment was carried out to increase the volume of air / medium pores in Kecheon black. Phosphoric acid is used as an acid, and 0.5 g of Kecheon black is added to 100 ml of a solution having an acid concentration of 20%, followed by stirring at 100 rpm for 0.5 hour at 25 ° C. After washing the distilled water and ethanol to neutralize the pH, they were dried at 25 ° C.

Example 2.

The procedure of Example 1 was repeated except that the concentration of acid was 40% and the stirring speed was 200 rpm.

Example 3.

The procedure was carried out in the same manner as in Example 2, except that the amount of Kecheon black was 1 g and the drying temperature was 50 ° C.

Example 4.

The procedure of Example 3 was repeated except that the concentration of the acid was 60%, the stirring temperature was 50 ° C, the stirring time was 3 hours, and the stirring speed was 300 rpm.

Example 5.

The procedure was carried out in the same manner as in Example 4, except that the amount of Kecheon black was 2 g and the drying temperature was 80 ° C.

Example 6.

The procedure of Example 5 was followed except that the acid concentration was 85%, the stirring temperature was 80 ° C, and the stirring speed was 400 rpm.

Example 7.

The procedure was carried out in the same manner as in Example 6, except that the amount of Kecheon black was 2 g, the stirring time was 6 hours, and the drying temperature was 100 ° C.

Example 8.

The procedure of Example 7 was repeated except that the stirring time was 24 hours and the stirring speed was 500 rpm.

Comparative Example 1

KEPCO black was directly measured without any treatment.

Comparative Example 2

The procedure was carried out in the same manner as in Example 6, except that the kind of acid was acid-treated with phosphoric acid, nitric acid having a concentration of 60%.

Comparative Example 3

The procedure was carried out in the same manner as in Example 6, except that the kind of acid was acid-treated with sulfuric acid having a concentration of 98% in phosphoric acid.

Measurement example 1. Pore characteristics of new carbon nanomaterial

The pore characteristics of the carbon nanomaterial prepared in the present invention at 77 K, 1 bar through BEL-SORP Analyzer (BEL Co., Ltd., Japan) are specified and the nitrogen adsorption isotherm is shown in FIG.

Measurement example 2. Pore size distribution of new carbon nanomaterial

The pore size distribution of the carbon nanomaterial prepared in the present invention was measured at 77 K, 1 bar nitrogen adsorption isotherm through BEL-SORP Analyzer (BEL Co., Ltd., Japan) and is shown in FIG.

The production conditions of Kecheon black in which atmospheric / mesopore pores are expressed according to an embodiment of the present invention Sample name Types of mountains Concentration of acid (%) Quantity of ketjen black (g) Stirring temperature
(° C) Stirring time
(h) Stirring speed (rpm) Drying temperature
(° C) Example 1 H 3 PO 4 20 0.5 25 0.5 100 25 Example 2 H 3 PO 4 40 0.5 25 0.5 200 25 Example 3 H 3 PO 4 40 One 25 0.5 200 50 Example 4 H 3 PO 4 60 One 50 3 300 50 Example 5 H 3 PO 4 60 2 50 3 300 80 Example 6 H 3 PO 4 85 2 80 3 400 80 Example 7 H 3 PO 4 85 3 80 6 400 100 Example 8 H 3 PO 4 85 3 80 24 500 100 Comparative Example 1 - - - - - - Comparative Example 2 HNO 3 60 2 80 3 400 80 Comparative Example 3 H 2 SO 4 98 2 80 3 400 80

       The volume of atmospheric / medium pores of Kecheon black in which atmospheric / mesopore pores are expressed according to an embodiment of the present invention Volume of atmospheric air (cm 3 / g) Volume of medium pore (cm 3 / g) Example 1 1.054 2.024 Example 2 1.120 2.035 Example 3 1.153 2.069 Example 4 1.340 2.120 Example 5 1.362 2.241 Example 6 1.675 2.227 Example 7 0.724 1.852 Example 8 0.722 1.780 Comparative Example 1 1.046 2.044 Comparative Example 2 1.223 1.948 Comparative Example 3 1.350 2.017

Measurement results.

Referring to FIG. 1, the nitrogen adsorption amount of Example 6 is higher than that of Comparative Example 1 at a point where the relative pressure is 0.9 or more, which indicates that the air vacancy volume of Example 6 is larger.

Referring to FIG. 2, it can be seen that the volume of Example 6 is larger than that of Comparative Example 1 in the vicinity of 20 to 80 nm of the graph.

Having described specific portions of the present invention in detail, those skilled in the art will appreciate that these specific embodiments are merely preferred embodiments and that the scope of the present invention is not limited thereby. something to do. Accordingly, the actual scope of the present invention will be defined by the appended claims and their equivalents.

Claims (6)

(1) carrying 1 to 2 g of Ketjen Blacks per 100 mL of a 60 to 85% phosphoric acid solution;
(2) acid-treating the mixture containing Ketjen Blacks at 50 to 80 ° C in the step (1); And
(3) washing the acid-treated mixture to a pH of 6.5 to 7.5, and then drying the washed mixture.
delete delete delete delete A carbon nanomaterial produced by the method of claim 1.

KR1020150142728A 2015-10-13 2015-10-13 Manufacturing method of carbon blakcs containing macro/meso pore structures KR101811015B1 (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100708732B1 (en) * 2005-11-26 2007-04-17 삼성에스디아이 주식회사 Anode for fuel cell, manufacturing method thereof, and fuel cell employing the same
US20080113859A1 (en) * 2006-05-08 2008-05-15 University Of South Carolina Composite catalysts supported on modified carbon substrates and methods of making the same

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100708732B1 (en) * 2005-11-26 2007-04-17 삼성에스디아이 주식회사 Anode for fuel cell, manufacturing method thereof, and fuel cell employing the same
US20080113859A1 (en) * 2006-05-08 2008-05-15 University Of South Carolina Composite catalysts supported on modified carbon substrates and methods of making the same

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