KR101524610B1 - The method for manufacturing the high conductive carbon nano fiber and the carbon nano fiber made thereby - Google Patents
The method for manufacturing the high conductive carbon nano fiber and the carbon nano fiber made thereby Download PDFInfo
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- KR101524610B1 KR101524610B1 KR1020130055942A KR20130055942A KR101524610B1 KR 101524610 B1 KR101524610 B1 KR 101524610B1 KR 1020130055942 A KR1020130055942 A KR 1020130055942A KR 20130055942 A KR20130055942 A KR 20130055942A KR 101524610 B1 KR101524610 B1 KR 101524610B1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E60/13—Energy storage using capacitors
Abstract
The present invention relates to a method for producing a high conductivity PAN / pitch carbon composite fiber capable of producing an electrode having a high electrical conductivity and a high capacity through pyrolytic carbon doping and surface selective graphitization on the surface of PAN or pitch fibers, TECHNICAL FIELD The present invention relates to a highly conductive PAN / pitch carbon composite fiber, and a method of manufacturing the same, which comprises: 1) dissolving an acrylonitrile raw material to prepare a raw material solution; 2) spinning the raw material solution to produce carbon nanofibers; 3) acid-treating the carbon nanofibers; 4) pyrolytic carbon coating the acid-treated carbon nanofibers; 5) graphitizing the carbon-coated carbon nanofibers.
Description
TECHNICAL FIELD The present invention relates to a method for producing high-conductivity carbon nanofibers and a high-conductivity carbon nanofiber produced by the method. More particularly, the present invention relates to a method for producing high-conductivity carbon nanofibers having high electrical conductivity by means of pyrolytic carbon doping and surface selective graphitization To a method of manufacturing a high-conductivity PAN / pitch carbon composite fiber capable of producing a high-capacity electrode and a high-conductivity PAN / pitch carbon composite fiber produced thereby.
Generally, supercapacitors use electrostatic characteristics, so they are almost infinite in charge / discharge cycles compared to batteries using electrochemical reactions, and can be used semi-permanently. The charge / discharge speed of energy is very fast, It is more than a dozen times.
Therefore, due to the characteristics of super capacitors that can not be realized with conventional chemical battery batteries, application fields of supercapacitors are gradually expanding throughout the industry. Particularly, in the field of next-generation environmentally-friendly vehicles such as electric vehicles (EV), hybrid electric vehicles (HEV) or fuel cell vehicles (FCV) The utility of supercapacitors is increasing day by day.
That is, supercapacitors are used as an auxiliary energy storage device in combination with a chemical battery battery, so that supercapacitors take charge of momentary energy supply and absorption, and the average energy supply of the vehicle is controlled by the battery, And extension of the life of the storage system.
In addition, it can be used as an auxiliary power source in portable electronic parts such as mobile phones and video recorders, and its importance and usage are increasing day by day.
Such super capacitors are classified into electric double layer capacitors (EDLC) and redox capacitors (pseudo capacitors). In the EDLC, an electric double layer is formed on the surface to accumulate electric charges, and the water storage capacitor accumulates electric charges by a redox reaction of a metal oxide used as an active material.
However, there is a problem that the material of the water-storage capacitor is expensive because the material used as the metal oxide (in particular, ruthenium oxide) is expensive, and the material is not environmentally friendly at the time of disposal after use.
On the other hand, EDLC uses environmentally friendly carbon materials with excellent stability of the electrode material itself. These carbon electrode materials include activated carbon powder (ACP), carbon nanotube (CNT), graphite, vapor grown carbon fiber (VGCF), carbon aerogels, Carbon nanofibers (CNF) and activated carbon nanofibers (ACNF), which are produced by carbonizing polymers such as polyacrylonitrile (PAN) and polyvinylidene fluoride (PVdF) Nano Fiber) are used. In addition to the carbon material, a conductive material such as carbon black is added to impart conductivity.
The EDLC is generally composed of a current collector, an electrode, an electrolyte, and a separator. Electrolytes are filled between two electrodes electrically separated from each other by the separator. The current collector effectively charges or discharges the electrode. It plays a role. The activated carbon electrode used as the electrode material of the EDLC is a porous micropore having a large specific surface area. When (-) is attached to the activated carbon electrode, (+) ions dissociated from the electrolyte are poured into the pores of the activated carbon electrode (+) Layer, which charges the charge while forming an electric double layer with a negative (-) layer formed at the interface of the activated carbon electrode.
The storage capacity of such an EDLC capacitor is highly dependent on the structure and physical properties of the activated carbon electrode. The required characteristics include a large specific surface area, a small internal resistance of the material itself, and a high density of carbon material .
However, conventionally, electrode materials having excellent electric conductivity and large capacitance have not been developed, and research and development thereof have been urgently required.
TECHNICAL PROBLEM TO BE SOLVED TO PROBLEM TO BE SOLVED: To provide a high-conductivity PAN / pitch carbon fiber composite material capable of producing electrodes having high electrical conductivity and increased capacity through pyrolytic carbon doping and surface selective graphitization on the surface of PAN or pitch fibers Method and a highly conductive PAN / pitch carbon composite fiber produced thereby.
According to an aspect of the present invention, there is provided a method of manufacturing a high-conductivity conductive PAN / pitch carbon composite fiber, comprising the steps of: 1) dissolving an acrylonitrile raw material to prepare a raw material solution; 2) spinning the raw material solution to prepare a polymer precursor fiber, and subjecting the polymer precursor fiber to an unfused and carbonized heat treatment to produce carbon nanofibers; 3) acid-treating the carbon nanofibers; 4) pyrolytic carbon coating the acid-treated carbon nanofibers; 5) graphitizing the carbon-coated carbon nanofibers.
In the step 1), the acrylonitrile raw material is preferably dissolved in DMF (DiMethyl Formamide) solution.
Also, in the step 2), it is preferable to produce carbon nanofibers using electrospinning.
And 4)
a) heating the acid-treated carbon nanofibers to 700 ° C at a heating rate of 10 ° C / min; b) pyrolysis carbon coating for 3 hours while supplying LPG gas at 200cc / min at a temperature of 700 ° C The method comprising the steps of:
In the present invention, in the step 5), the argon (Ar) gas is preferably introduced at a rate of 200 cc / min, elevated to 2800 ° C at a heating rate of 10 ° C / min and graphitized for 10 minutes Do.
The present invention also provides high-conductivity carbon nanofibers, electrodes for capacitors, and capacitors manufactured by the above-described method for manufacturing high-conductivity carbon nanofibers.
The high-conductivity carbon nanofibers produced by the method for producing high-conductivity carbon nanofibers of the present invention can remarkably lower the resistance of the capacitor electrodes even if a small amount is used, and the high-conductivity carbon nanofibers can be obtained through a graphitization process at a relatively low temperature. And has an excellent effect of increasing the capacitance of the capacitor electrode because of its excellent electric conductivity.
Particularly, as can be seen from FIG. 2 (scanning electron microscope (SEM) photograph of the high-conductivity carbon nanofibers of the present invention), the high-conductivity carbon nanofiber according to the present invention has an average fiber diameter of about 428 nm,
As can be seen from FIG. 3 (transmission electron microscope (TEM) photograph of the high-conductivity carbon nanofibers of the present invention), the carbon nanofiber itself is of the P-type, And it has a crystal structure similar to that of the grown T-type carbon nanofibers.
Therefore, the carbon nanofibers of the present invention are PC-coated on the surface of P-type carbon nanofibers and can be easily graphitized even at a relatively low temperature (2800 degrees). PC coating changes the surface of the surface from P-type to T-type with good electrical conductivity, which increases the electrical conductivity and increases the contact area with activated carbon. Due to these two synergistic effects, the carbon nanofibers of the present invention have characteristics in which the internal resistance and electrical conductivity of the electrode are increased and the capacity is increased.
FIG. 1 is a flow chart showing a process for producing a high-conductivity carbon nanofiber according to the present invention.
2 is a SEM photograph of the high-conductivity carbon nanofibers according to the present invention.
3 is a TEM photograph of the high-conductivity carbon nanofibers according to the present invention.
Fig. 4 shows electrical conductivity data of Examples 1 and 2 and Comparative Examples 1 and 2. Fig.
FIG. 5 shows sheet resistivity data of Examples 1 and 2 and Comparative Examples 1 and 2. FIG.
6 shows IR drop data of Examples 1 and 2 and Comparative Examples 1 and 2.
Fig. 7 shows battery capacity evaluation data of Examples 1 and 2 and Comparative Examples 1 and 2. Fig.
Hereinafter, the present invention will be described in detail with reference to the accompanying drawings.
First, the method for producing a highly conductive PAN / pitch carbon composite fiber of the present invention comprises the steps of 1) preparing a raw material solution by dissolving polyacrylonitrile (PAN) (S100). In this step S100, acrylonitrile is dissolved in a DMF solution to prepare a raw material solution.
Next, a step S200 of fabricating the carbon nanofibers by electrospinning the raw material solution prepared in the previous step S100 is performed. In step S200, the raw material solution is dissolved in a DMF solution, and the obtained raw material solution is electrospun at a distance of 30 cm at a distance of 30 cm to form polymer precursor fibers, and then the carbon nanofibers are prepared by insolubilizing and heat-treating the carbon fibers.
Next, the acid treatment of the carbon nanofibers (S300) proceeds. For example, in step S300, the produced carbon nanofibers can be acid-treated for 48 hours by mixing 100 ml of a 10% HCl solution per g of carbon nanofibers.
Next, the acid-treated carbon nanofibers are subjected to thermal decomposition carbon coating (S400). In this step S400, the carbon nanofibers are coated with pyrolytic carbon on the surface of the carbon nanofibers. Specifically, g) the carbon nanofibers subjected to the acid treatment are heated to 700 ° C at a heating rate of 10 ° C / min And (h) pyrolysis carbon coating for 3 hours while supplying LPG gas at a rate of 200 cc / min at a temperature of 700 캜 raised in the previous step (S300).
Finally, graphitizing the carbon-coated carbon nanofibers (S500) is performed. In this step S500, the argon (Ar) gas is preferably introduced at a rate of 200 cc / min, elevated to 2800 ° C at a rate of 10 ° C / min, and graphitized for 10 minutes.
Hereinafter, the results of comparing the examples of producing carbon nanofibers with the comparative examples actually produced according to the above-described manufacturing method will be described.
Example One : Of carbon nanofiber Produce
First, polyacrylonitrile is mixed with peracetyl acetate (Fe (Acc) 3 ) as a catalyst and dissolved in a 10 wt% DMF solution. Then, this solution is subjected to electrospinning at a distance of 30 cm at a voltage of 30 kV, and the carbon nanofibers are produced by heat treatment and immobilization.
The prepared carbon nanofibers are mixed with 100 ml of 10% HCl solution per 1 g of carbon nanofibers and subjected to acid treatment for 48 hours. The acid-treated carbon nanofibers are heated to 2800 ° C at 10 ° C / min with 200 cc / min of Ar, and graphitized at 2800 ° C for 10 min.
Carbon nanofibers were prepared through the above process.
Example 2: High electrical conductivity Of carbon nanofiber Produce
The same procedure as in Example 1 was carried out, except that PC coating was carried out before the graphitization treatment. That is, after the acid treatment, the temperature is raised to 700 ° C at 10 ° C / min (N 2 , 200cc / min) and the PC is coated with LPG gas at 200cc / min for 3 hours at 700 ° C. Ar is introduced at 200 cc / min, the temperature is raised to 2800 degrees at 10 ° C / min, and graphitization is performed at 2800 degrees for 10 minutes.
The high-conductivity carbon nanofibers were prepared through the above-mentioned procedures.
Comparative Example One
As a comparative example 1, a commercially available fibrous conductor of Showa Denko company was used.
Comparative Example 2
As a comparative example 2, a commercially available powdery conductive material of Timcal Co. was used
Hereinafter, results of comparison between the electrical conductivity, specific resistance, and characteristics of the electrodes prepared in Examples 1 and 2 and Comparative Examples will be described.
4 shows electrical conductivities of Examples 1 and 2 and Comparative Examples 1 and 2, and FIG. 5 shows sheet resistivities of Examples 1 and 2 and Comparative Examples 1 and 2. FIG. As shown in FIGS. 4 and 5, it can be seen that the electrical conductivity and the sheet resistivity value of Example 2 are superior to those of Example 1 and Comparative Examples 1 and 2.
FIG. 6 shows the IR drop of Examples 1 and 2 and Comparative Examples 1 and 2, and FIG. 7 shows the results of the battery capacity evaluation of Examples 1 and 2 and Comparative Examples 1 and 2. FIG. IR drop and cell capacity were evaluated by making a standard CR2032 coin cell. Electrode slurry was prepared by using activated carbon MSP-20 in weight ratio of activated carbon / conductive material / binder of 86/7 / 7wt.% And coated on aluminum foil. In addition, the electrolyte was charged and discharged in a voltage range of 2 to 3.8 V by using PC-system TEABF4 to evaluate the capacity.
As a result, as shown in FIGS. 6 and 7, the IR drop and the battery capacity of Example 2 were superior to those of Example 1 and Comparative Examples 1 and 2.
Claims (8)
2) spinning the raw material solution to prepare a polymer precursor fiber, and subjecting the polymer precursor fiber to an unfused and carbonized heat treatment to produce carbon nanofibers;
3) acid-treating the carbon nanofibers;
4) pyrolytic carbon coating the acid-treated carbon nanofibers;
5) graphitizing the carbon-coated carbon nanofibers,
The step (4)
a) heating the acid-treated carbon nanofibers to 700 ° C at a heating rate of 10 ° C / min;
b) pyrolysis carbon coating for 3 hours while supplying LPG gas at a rate of 200 cc / min at a temperature of 700 캜,
The step (5)
Wherein the graphite is subjected to a graphitization treatment at a heating rate of 10 DEG C / min to 2800 DEG C in a state where argon (Ar) gas is supplied at a rate of 200 cc / min. Gt;
Wherein the acrylonitrile raw material is dissolved in DMF (dimethyl formamide) solution.
Wherein the carbon nanofibers are prepared by using an electrospinning method.
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| KR100675923B1 (en) * | 2005-12-01 | 2007-01-30 | 전남대학교산학협력단 | Metal oxide incorporated activated carbon nanofibers by co-electrospinning, their applications of electrode for supercapacitors, and the producing method of the same |
| KR20130048934A (en) * | 2011-11-03 | 2013-05-13 | (주)아모레퍼시픽 | PVDF NANOFIBROUS MEMBRANE WITH HIGH RATIO OF β-PHASE, PIEZOELECTRIC AND FERROELECTRIC PROPERTIES, AND MANUFACTURING METHOD OF THE SAME |
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| KR100675923B1 (en) * | 2005-12-01 | 2007-01-30 | 전남대학교산학협력단 | Metal oxide incorporated activated carbon nanofibers by co-electrospinning, their applications of electrode for supercapacitors, and the producing method of the same |
| KR20130048934A (en) * | 2011-11-03 | 2013-05-13 | (주)아모레퍼시픽 | PVDF NANOFIBROUS MEMBRANE WITH HIGH RATIO OF β-PHASE, PIEZOELECTRIC AND FERROELECTRIC PROPERTIES, AND MANUFACTURING METHOD OF THE SAME |
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