KR101370868B1 - Carbonfiber by polyfurfuryl alcohol and its manufacturing method for thereof - Google Patents

Abstract

   The present invention provides a carbon fiber using a polyperfuryl alcohol and a method of manufacturing the same, and carbon fiber of the present invention can significantly increase the specific amount compared to graphite, which is a conventional negative electrode material, in particular polyacrylonitrile alone Compared with the carbon fiber used as the mechanical properties, the initial irreversible capacity and cycle characteristics can be improved. In addition, carbon fiber using polyperfuryl alcohol shows a very high light conversion efficiency as a counter electrode for dye-sensitized solar cells.

Description

   Carbon fiber using polyperfuryl alcohol and its manufacturing method {Carbonfiber by polyfurfuryl alcohol and its manufacturing method for

   The present invention provides a carbon fiber characterized in that the carbon precursor by electrospinning the fibrous precursor composition comprising a carbon precursor, polyperfuryl alcohol, and a polymer resin or metal precursor, heat treatment, and then carbonized it It is about a method.

   At present, with the increase in the capacity of mobile devices and the development of electric vehicles, interest in lithium secondary batteries having high performance and high efficiency energy density is increasing. Among the carbon-based materials, carbon materials can be classified into graphite based crystals and carbon based amorphous carbons according to the structure of the lithium secondary battery. The graphite based natural graphite, artificial graphite, graphitized meso Carbon microbeads, mesophase pitch carbon fibers, and the like are proposed, and carbon-based carbon dioxide, various types of coke, mesocarbon microbeads, mesophase pitch carbon fibers, vapor grown carbon fibers, poly Acrylonitrile (PAN) -based carbon fibers, thermosetting resin carbides and the like have been proposed.

The graphite-based material has advantages of excellent reversible characteristics and low potential planar surface, but is difficult in manufacturing conditions, expensive, and has a disadvantage in that its capacity is limited to 372 mAh / g. Amorphous carbon has an advantage of having a large discharge capacity and excellent suitability for a solvent, but it is still difficult to apply a large capacity lithium secondary battery because the initial irreversible capacity is very large and the potential flatness is not long.

   Polyacrylonitrile, which is mainly used as a precursor of amorphous carbon, is mainly made of carbon fiber by electrospinning, and carbon fiber produced at 700 to 800 ° C. has a very high initial capacity of 800 mAh / g, but at the same time 50% Very high irreversible capacity over has the disadvantages seen. This irreversible capacity is due to the formation of irreversible SEI due to the high specific surface area of the polyacrylonitrile carbon fiber, and the specific surface area must be lowered to reduce this. In addition, polyacrylonitrile carbon fiber has a disadvantage in that the mechanical strength drops when carbonizing at a high temperature, and commercialization as a negative electrode of a secondary battery is still limited.

   Other amorphous carbons include tar, pitch, phenol resins, furan resins, or furfuryl alcohols. In particular, perfuryl alcohols are easily polymerized into polyfuryl alcohols at constant temperature, acid and base conditions. Excellent compatibility with polymers and solvents. The polymerized perfuryl alcohol resin is one of thermosetting resins and has a high residual carbon content, and is actively used for the synthesis of carbide compounds, mesoporous materials, capsule structures, and the like.

   In particular, the perfuryl alcohol resin is a method for producing nanoporous carbon having improved mechanical strength, and nanoporous carbon (Korean Patent Publication No. 2004-0042142) produced by the same, and a carbon material having nanopores prepared using inorganic template particles Electric double layer capacitors (Korean Patent Publication No. 2001-0107049) used as electrodes, methods for producing nanoporous carbon materials using inorganic molds of sol-gel reactions for supercapacitors (Korea Patent Publication No. 2002-0097295), etc. Synthesis of nanostructures and removal of nanostructures has the disadvantage of going through complicated steps to obtain pure carbon structures.

(Korean Patent Publication No. 2004-0042142) (Korean Patent Publication No. 2001-0107049) (Korean Patent Publication No. 2002-0097295)

The present invention is to solve the above problems of the prior art

(1) the capacity and mechanical strength of the negative electrode material for secondary batteries can be improved compared to carbon fiber using polyacrylonitrile (carbon precursor) alone;

(2) dramatically improved initial irreversible capacity, resulting in high irreversible capacity and very good cycle stability;

(3) The present invention provides a carbon fiber using polyperfuryl alcohol, which is a negative electrode active material of a lithium secondary battery, which can exhibit a very good light conversion efficiency as a counter electrode of a dye-sensitized solar cell, and a manufacturing method thereof.

The present invention provides a carbon fiber using polyperfuryl alcohol which can replace graphite used as a negative electrode material of a lithium secondary battery.

The present invention also provides a method for producing carbon fibers using polyperfuryl alcohol.

Method for producing a carbon fiber using a polyperfuryl alcohol according to the present invention

(a) electrospinning a spinning composition comprising polyperfuryl alcohol to prepare a fibrous precursor;

(b) heat treating the fibrous precursor prepared in step (a) in the presence of oxygen to produce an oxidative stabilized fibrous precursor; And

(c) carbonizing the oxidative stabilized fibrous precursor to produce carbon fibers;

Method of producing a carbon fiber comprising a.

The spin composition further comprises one or two or more of a carbon precursor, a polymer resin, or a mixture thereof. The weight ratio of polyperfuryl alcohol to carbon precursor in the spinning composition is from 1: 0.01 to 100; The weight ratio of the polyperfuryl alcohol to the polymer resin is 1: 0.01 to 20 weight ratio of carbon fiber manufacturing method, characterized in that.

 In addition, the weight ratio of the spinneret to the metal precursor is a method for producing a carbon fiber, characterized in that further comprises a 0.015 to 0.5 weight ratio.

The 'polyperfuryl alcohol' is prepared by stirring for 6 to 24 hours at 100-140 ℃ using a perfuryl alcohol and 3 to 10% by weight of NiCl2 or CoCl2 catalyst, the prepared polyperfuryl alcohol itself viscosity Because of this, electrospinning is possible without adding a solvent. In addition, since the polyperfuryl alcohol has very good miscibility with the solvent and the polymer, it is not necessary to dilute the solvent separately and mix with the polymer solution.

The polyperfuryl alcohol is resorcinol-formaldehyde-gel, phenol-formaldehyde-gel, phenol resin, melamine-formaldehyde-gel, epoxy resin (Epoxy One or more than one of resin, pitch, and sucrose is preferable, but not limited thereto.

The 'polymer resin' refers to a 'polymer resin' that can help form carbon fibers by improving the viscosity and processability of the fibrous precursor composition during electrospinning. The polymer is completely burned during heat treatment and disappears without leaving carbon. Refers to.

The polymer resin is one selected from polyvinyl alcohol (PVA, polyvinyl alcohol), polyvinyl acetate (PVAc, polyvinyl acetate), polymethyl methacrylate (PMMA, polymethyl methacrylate), polypyrrolidone (PVP), polyethylene oxide (PEO) Or a mixture of two or more thereof is preferred but not limited thereto.

  The 'carbon precursor' used in the present invention refers to a material that can be converted into specific carbon by heat treatment, and the carbonization yield may be different for each material.

 The carbon precursor is polyacrylonitrile (PAN), cellulose, glucose, polyvinyl chloride (PVC), polyacrylic acid, polylactic acid, polyethylene oxide, polypyrrole, polyimide, polyamideimide (PAI), polyaramid, polybenzyl The use of one or two or more mixtures selected from the group consisting of midazoles, phenol resins and pitches, polyaniline, poly (3,4-ethylenedioxythiophene) (PEDOT), polythiophene, and polythiophene derivatives Preferred but not limited to this.

The spinning composition is a polar solvent other than water, dimethylformamide (DMF), dimethylacetamide (DMAc), tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), gamma butyrolactone, N-methylpyrrolidone, Chloroform, toluene, acetone or mixtures thereof can be used. More preferably, one or more of dimethylformamide (DMF), dimethylacetamide (DMAc) and tetrahydrofuran (THF) may be further included. The weight part of the solvent may include a carbon precursor, a polymer resin, or a mixture thereof. It is preferable that it is 0.05-1 weight part with respect to a weight part.

In addition, the weight average molecular weight of the polymer resin is preferably 50,000 to 500,000. If the weight average molecular weight is less than 50,000, the viscosity of the fibrous precursor composition is low, and if it exceeds 500,000, the viscosity is high, which is not preferable. The most important factor in the carbon fiber manufacturing step using electrospinning is the appropriate viscosity of the composition. Since the electrospinning of polyperfuryl alcohol according to the present invention may exhibit a desired viscosity, it is possible to produce a carbon fiber for a lithium secondary battery negative electrode of high strength, high capacity.

   In addition, the metal precursor of the present invention is copper (Cu), nickel (Ni), cobalt (Co), tin (Sn), silicon (Si), iron (Fe), antimony (Sb), aluminum (Al), or bismuth A salt or organometallic compound containing at least one metal selected from (Bi).

When the radiation composition of the present invention includes the metal precursor, it is possible to express high capacity and high light conversion efficiency as a negative electrode material for a lithium secondary battery and a counter electrode of a dye-sensitized solar cell. The composition is stirred to homogenize or homogenized by applying a temperature as needed, and then put into a syringe (syringe) to which a needle is attached, and electrospun at a voltage of 20 to 30 kV to prepare a fibrous precursor, which is then 220 to 300. The temperature is raised to ℃, and the oxidation is stabilized for 0.5 to 10 hours in the air atmosphere (in the presence of acid). The thermoplastic resin is melted when carbonized and activated at a high temperature, or fusion between the spinning composition occurs. To prevent this, the thermoplastic resin is converted into a thermosetting resin through an oxidative stabilization step. That is, the oxidation stabilization step is a process of oxidizing the fibrous precursor from the surface in order to prevent the fusion and thermal melting of the fibrous precursor in the high temperature carbonization, activation step by converting the thermoplastic resin into a thermosetting resin. If carbonization or activation is performed directly without performing the oxidative stabilization step, exothermic reactions such as ring opening and dehydrogenation proceed rapidly and are burned rather than carbonized. The oxidative stabilization process may be omitted depending on the content of polyperfuryl alcohol.

   After the stabilization process to maintain the size and structure of the fibrous precursor is subjected to a carbonization step of high temperature heating to remove the volatile non-carbon components or increase the surface area. Specifically, the step of carbonizing the oxidative stabilized fibrous precursor at 100 ~ 1000 ℃ in an inert atmosphere or vacuum state to produce a carbon fiber.

The present invention provides a carbon fiber using a polyperfuryl alcohol prepared by the above production method. When the carbon fiber using the polyperfuryl alcohol is used as a negative electrode of a lithium secondary battery, the capacity of the carbon fiber negative electrode material prepared by electrospinning alone using polyacrylonitrile (carbon precursor) prepared under the same temperature conditions Is increased and shows excellent cycle characteristics. Also, when carbon fiber using polyperfuryl alcohol is used as a counter electrode for dye-sensitized solar cells, the light conversion efficiency is much higher than that of the counter electrode material of carbon fiber prepared by electrospinning polyacrylonitrile alone at the same temperature condition. It shows high characteristics. Accordingly, the present invention provides a lithium secondary battery electrode material and a counter electrode material of a dye-sensitized solar cell including the carbon fiber.

Carbon fiber using the polyperfuryl alcohol of the present invention can not only significantly increase the specific capacity compared to graphite, which is a conventional negative electrode material, but also mechanical properties compared to carbon fibers prepared by electrospinning polyacrylonitrile alone. And the initial irreversible capacity is improved, and the cycle characteristics are also excellent. In addition, since carbon fiber using polyperfuryl alcohol shows very good light conversion efficiency, it is applicable to the counter electrode material of a dye-sensitized solar cell. In addition, it is possible to control the diameter of the fiber, the surface roughness of the fiber, the porous structure and the like according to the type and content of the polymer to be added. Compared with the conventional electrode material using particulate form, it is manufactured in the state of fiber web, which enables fast electron transfer, requires no active materials, binders, conductive agents, other solvents, and additional facilities, and makes the process simple. And because it is easy to handle, the expected effect is very large as an electrode material and a catalyst.

1 and 2 are scanning micrographs of carbon fibers using polyperfuryl alcohol / polyacrylonitrile prepared in Example 1. FIG.
3 to 5 are scanning micrographs of carbon fibers using polyperfuryl alcohol / polyacrylonitrile / polymethylmethacrylate prepared in Example 2.
6 to 8 are scanning micrographs of carbon fibers using polyperfuryl alcohol / polyacrylonitrile / polyvinylpyrrolidone prepared in Example 3. FIG.
9 and 10 are scanning micrographs of carbon fibers using polyperfuryl alcohol, carbon precursor (polyacrylonitrile), and metal precursor (Ni acetate) prepared in Example 4. FIG.
11 and 12 are scanning micrographs of carbon fibers using polyperfuryl alcohol and polymer resin (polyvinylpyrrolidone; PVP) prepared in Example 5. FIG.
FIG. 13 is a scanning micrograph of carbon fibers prepared by electrospinning polyacrylonitrile prepared in Comparative Example 1 alone. FIG.
Figure 14 shows the charge and discharge capacity and cycle characteristics according to the content of the carbon fiber using the polyperfuryl alcohol / polyacrylonitrile prepared in Example 1.
Figure 15 shows the results of the Coulomb efficiency characteristics for each carbon fiber content using the polyperfuryl alcohol / polyacrylonitrile prepared in Example 1.
Figure 16 shows the charge and discharge capacity and cycle characteristics of the carbon fiber using the polyacrylonitrile prepared by Comparative Example 1 alone.
Figure 17 shows the coulombic efficiency characteristics of the carbon fiber using the polyacrylonitrile prepared by Comparative Example 1 alone.
FIG. 18 shows scanning micrographs and transmission micrographs of carbon fibers using polyperfuryl alcohol and polymer resin (polyvinylpyrrolidone; PVP) prepared in Example 6. FIG.
FIG. 19 shows the counter electrode characteristics of a dye-sensitized solar cell of carbon fiber using the polyperfuryl alcohol / polyvinylpyrrolidone of Example 6. FIG.

Hereinafter, preferred embodiments of the present invention will be described in order to facilitate understanding of the present invention. However, the following examples are provided only for the purpose of easier understanding of the present invention, and the present invention is not limited thereto.

[evaluation]

   Physical properties measuring method according to an embodiment of the present invention is as follows.

Diameter distribution and surface image were measured by scanning microscope (FE-SEM, Hitachi, S-4700), and the charge / discharge capacity and cycle characteristics of lithium secondary battery were lithium (Li) metal / separator / poly Coin cell composed of carbon fiber, LiPF6 1: 1 vol% EC DMC liquid electrolyte using perfuryl alcohol was prepared and analyzed, and charging and discharging experiments were performed using a charger. In addition, N719-sensitized nanoporous TiO2 electrodes were used for the evaluation of the dye-sensitized solar cell counter electrode, and 0.6M DMPImI, 0.1 LiI, 0.05 M I2 and t-butylpyridineandacetonitrile were used as electrolytes.

Example 1 Preparation of Carbon Fiber Using Polyperfuryl Alcohol and Carbon Precursor (Polyacrylonitrile)

1 g of polyacrylonitrile resin having a weight average molecular weight of 150,000 was added to 7 g of dimethylformamide (N, N-dimethylforamide), and then dissolved at 120 ° C. for 5 hours to prepare a polyacrylonitrile solution (A).

Polyperfuryl alcohol (B) was prepared by stirring at 120 ° C. for 12 hours using perfuryl alcohol and 5 wt% of NiCl 2 catalyst.

Polyperfuryl alcohol 1 g (B) was added to the polyacrylonitrile solution (A) at room temperature, followed by stirring for 3 hours to prepare a polyperfuryl alcohol / polyacrylonitrile resin solution (C).

At this time, the weight ratio (%) of the carbon precursor (polyacrylonitrile) and polyperfuryl alcohol was 1: 1. The homogenized polyperfuryl alcohol / polyacrylonitrile resin solution (C) was electrospun. At this time, the electrospinning conditions were put into the solution (C) in a 10ml syringe attached to a 0.5mm needle was electrospun at a voltage of 20 kV. At this time, the distance between the needle and the current collector was maintained at 17cm and the dissolution rate of the solution (C) was 1ml / h. The separated fibrous precursor was oxidatively stabilized at 280 ° C. for 5 hours in an air atmosphere. At this time, it heated up at 1 degree-C / min, and hold | maintained at 280 degreeC for 5 hours. After sufficiently oxidative stabilization, carbonization was performed at 800 ° C. for about 1 hour to prepare carbon fibers.

Example 2 Preparation of Carbon Fiber Using Polyperfuryl Alcohol, Carbon Precursor (Polyacrylonitrile), and Polymer Resin (Polymethylmethacrylate; PMMA)

   1 g of a polymethyl methacrylate resin having a weight average molecular weight of 130,000 was added to 7 g of dimethylformamide (N, N-dimethylforamide), and then dissolved at 120 ° C. for 5 hours to give a polymethyl methacrylate (PMMA) resin solution (D ) Was prepared.

Carbon fibers were prepared in the same manner as in Example 1, except that the weight ratio of polyperfuryl alcohol (PFA), polyacrylonitrile resin (PAN), and polymethylmethacrylate (PMMA) was 1: 1: 1. .

Example 3 Preparation of Carbon Fiber Using Polyperfuryl Alcohol, Carbon Precursor (Polyacrylonitrile), and Polymer Resin (Polyvinylpyrrolidone; PVP)

1 g of polyvinylpyrrolidone resin having a weight average molecular weight of 200,000 was added to 7 g of dimethylformamide (N, N-dimethylforamide), and then dissolved at 120 ° C. for 5 hours to prepare a polyvinylpyrrolidone resin solution (E). It was.

Carbon fiber was prepared in the same manner as in Example 1 except that the weight ratio of polyperfuryl alcohol (PFA), polyacrylonitrile resin (PAN), and polyvinylpyrrolidone (PVP) was 1: 1: 1. .

Example 4 Preparation of Carbon Fiber Using Polyperfuryl Alcohol, Carbon Precursor (Polyacrylonitrile), and Metal Precursor (Ni Acetate)

After adding a certain amount of Ni acetate to the solution C of Example 1, the mixture was stirred at 120 ° C. for at least 3 hours, cooled, and the prepared solution (F) was electrospun. At this time, the electrospinning conditions were put into the solution (F) in a 10ml syringe attached to a 0.5mm needle was electrospun at a voltage of 20 kV. In this case, the distance between the needle and the current collector was maintained at 17 cm, and the dissolution rate of the solution (F) was 1 ml / h. When fibers were accumulated in the current collector, the nonwoven fabric was separated and separated.

   Fibrous precursors using the separated Ni acetate / poly perfuryl alcohol and polyacrylonitrile resin were oxidatively stabilized at 280 ° C. for 5 hours in an air atmosphere. At this time, it heated up at 1 degree-C / min, and hold | maintained at 280 degreeC for 5 hours. After sufficiently oxidative stabilization, after carbonizing at 900 ° C. for 1 hour, carbon fibers using NiO and polyperfuryl alcohol were prepared.

Example 5 Preparation of Carbon Fiber Using Polyperfuryl Alcohol and Polymer Resin (Polyvinylpyrrolidone; PVP)

A polymer solution (D) was prepared by adding 1 g of polyvinylpyrrolidone resin having a weight average molecular weight of 200,000 to 7 g of dimethylformamide (N, N-dimethylforamide) and dissolving at 120 ° C. for 5 hours. At this time, the weight ratio of polyperfuryl alcohol (A) and polyvinylpyrrolidone (PVP) was set to 95: 5, and carbonized at 800 ° C. to prepare carbon fibers.

Example 6 Preparation of Counter Electrode Using Carbon Fiber Prepared in Example 3

The polyvinylpyrrolidone resin solution of Example 3 was added to a 95% by weight solution of polyperfuryl alcohol (B) of Example 1 prepared by stirring at 120 ° C for 12 hours using perfuryl alcohol and 5 wt% of NiCl2 catalyst. E) a 5 wt% solution was mixed and electrospun and carbonized at 700 ° C. to be used as a counter electrode of a dye-sensitized solar cell. The counter electrode was prepared by pulverizing carbon fiber, dispersing it in isopropyl alcohol (IPA), and then coating it on FTO by spraying. In addition, in the preparation of the carbon fiber, the mixed solution was immediately carbonized at 700 ° C. without undergoing an electrospinning technique to obtain polyperfuryl alcohol / polyvinylpyrrolidone (Ni / CP) carbon, and only perfuryl alcohol was used. The carbon was immediately carbonized at 700 ° C. to obtain polyperfuryl alcohol carbon (Ni-free CP). A counter electrode of a solar cell was prepared by the above-described method.

Comparative Example 1. Preparation of carbon fiber using carbon precursor (polyacrylonitrile) alone

Polyacrylonitrile single carbon nanofibers were prepared in the same manner as in Example 1, except that no polypiperidyl alcohol was added.

Scanning micrographs of carbon fibers using polyperfuryl alcohol and carbon precursor (polyacrylonitrile) prepared in Example 1 are shown in FIGS. 1 and 2.

As shown in FIGS. 1 and 2, in the case of carbon fibers using polyperfuryl alcohol prepared by heat treatment at 800 ° C., carbon fibers having a very uniform size were produced. It seems to be due to the good miscibility between nitriles.

3 to 5 are scanning micrographs of carbon fibers using polyperfuryl alcohol prepared according to Example 2, polyacrylonitrile, and polymethylmethacrylate, and the surface roughness of the fiber is increased according to the addition of polymethylmethacrylate. Increasingly, it was possible to produce hollow fiber type carbon fiber.

6 to 8 are scanning micrographs of carbon fibers using polyperfuryl alcohol, polyacrylonitrile, and polyvinylpyrrolidone prepared according to Example 3, wherein fiber surface roughness according to the addition of polyvinylpyrrolidone It can be seen that increased.

9 and 10 are carbon fiber obtained by electrospinning the polyperfuryl alcohol, carbon precursor (polyacrylonitrile), and metal precursor (Ni acetate) prepared in Example 4, and carbonization at 900 ℃ after oxidation stabilization By micrograph, it was possible to produce carbon fibers using NiO and polyperfuryl alcohol in the form of very uniform carbon fibers.

11 and 12 are scanning micrographs of carbon fibers using polyperfuryl alcohol and polymer resin (polyvinylpyrrolidone; PVP) prepared in Example 5, and it can be seen that the surface of the fibers is very smooth. It can be confirmed that a carbon fiber having a constant diameter was obtained.

13 is a scanning micrograph of the carbon fiber using the polyperfuryl alcohol prepared in Example 5 and a polymer resin (polyvinylpyrrolidone; PVP), the average diameter is about 300nm to represent a carbon fiber according to the present invention It was found that the fiber diameter was larger than that of the fiber.

FIG. 14 shows charge and discharge capacity and cycle characteristics when carbon fibers using polyperfuryl alcohol and polyacrylonitrile prepared in Example 1 were used as electrodes. In addition, Figure 15 is the Coulomb efficiency when used as a negative electrode. When the weight ratio of polyperfuryl alcohol and polyacrylonitrile is 1: 2.33, the initial discharge capacity is 959.9 mAh / g, and the weight ratio of polyperfuryl alcohol and polyacrylonitrile is 1: 1 at the 30th cycle of 489 mAh / g. It can be seen that when the higher capacity. In addition, the initial coulombic efficiency also showed a higher tendency of 58.34% when the weight ratio of polyperfuryl alcohol and polyacrylonitrile was 1: 2.33.

16 and 17 show the negative electrode characteristics of the lithium secondary battery of the carbon fiber using the polyperfuryl alcohol and the polymer resin (polyvinylpyrrolidone; PVP) of Example 5. 9 and 10, the carbon fiber using polyacrylonitrile alone had a discharge capacity of 826 mAh / g for the first cycle and 386 mAh / g for the 30th cycle. In addition, it can be seen that the initial coulombic efficiency is about 56%, which shows lower electrochemical properties compared to the carbon fiber to which polyperfuryl alcohol is added. This is because the polyperfuryl alcohol is well mixed with polyacrylonitrile, which reduces the formation of micropores, thereby reducing the formation of SEI. The non-covalent electron pair of oxygen in the polyperfuryl alcohol participates in the red ion reaction and redox reaction. Seems.

Therefore, carbon fiber using polyperfuryl alcohol could be easily produced by using an electrospinning technique, and the diameter, fiber surface roughness, and porous structure of the fiber were developed according to the type and content of the thermoplastic polymer mixed with the polyfuryl alcohol. Carbon fibers could be prepared. In addition, carbon fiber using polyperfuryl alcohol containing a metal or metal oxide could be prepared, and carbon fiber using polyperfuryl alcohol was used as a negative electrode material for a lithium secondary battery. It can be seen that it represents a higher specific capacity than.

FIG. 18 shows SEM and TEM images of carbon fibers (e-Ni / CNF) using Ni and polyperfuryl alcohol, and FIG. 19 shows carbon fibers (e-Ni / CNF) and Ni using polyperfuryl alcohol. And the relative electrode properties of carbon (Ni / CP) using polyperfuryl alcohol, carbon (Ni-free CP) using polyperfuryl without Ni, and Pt state electrode dye-sensitized solar cell without electrospinning. As can be seen in FIG. 18, in the case of carbon fibers using polyperfuryl alcohol, very small size Ni particles were dispersed, and as shown in FIG. 19, carbon fibers using polyperfuryl alcohol according to the present invention were used in dye-sensitized solar cells. When used as a counter electrode, it can be seen that the photoelectric efficiency is superior to that of the conventional Pt counter electrode, and also has an excellent light conversion efficiency compared to the powder type Ni / CP and Ni-free CP.

Claims (15)

(a) electrospinning a spinning composition comprising polyperfuryl alcohol and a metal precursor to prepare a fibrous precursor;
(b) heat treating the fibrous precursor prepared in step (a) in the presence of oxygen to produce an oxidative stabilized fibrous precursor; And
(c) carbonizing the oxidative stabilized fibrous precursor to produce carbon fibers;
Method for producing a carbon fiber comprising a. delete The method of claim 1,
The spinning composition further comprises a carbon precursor, a polymer resin or a mixture thereof. The method of claim 3, wherein
The carbon precursor is polyacrylonitrile (PAN), cellulose, glucose, polyvinyl chloride (PVC), polyacrylic acid, polylactic acid, polyethylene oxide, polypyrrole, polyimide, polyamideimide (PAI), polyaramid, polybenzyl One or two or more selected from the group consisting of midazole, phenol resins and pitches, polyaniline, poly (3,4-ethylenedioxythiophene) (PEDOT), polythiophene, and polythiophene derivatives Method for producing carbon fiber. The method of claim 3, wherein
The polymer resin is polyvinyl alcohol (PVA, polyvinyl alcohol), polyvinyl acetate (PVAc, polyvinyl acetate), polymethyl methacrylate (PMMA, polymethyl methacrylate), polyvinylpyrrolidone (PVP), polyethylene oxide (PEO) Method for producing a carbon fiber, characterized in that any one or more selected from. The method of claim 3, wherein
The weight average molecular weight of the polymer resin is 50,000 to 500,000 method for producing carbon fiber. The method of claim 3, wherein
The spinning composition comprises N, N-dimethylformamide (DMF), dimethylacetamide (DMAc), tetrahydrofuran (THF), dimethylsulfoxide (DMSO), gamma butyrolactone, N-methylpyrrolidone, chloroform, Method for producing a carbon fiber characterized in that it further comprises at least one solvent selected from toluene and acetone. 8. The method of claim 7,
The weight part of the solvent is 0.05 to 1 part by weight based on 1 part by weight of the carbon precursor, the polymer resin or a mixture thereof. delete The method of claim 1,
The metal precursor is selected from among copper (Cu), nickel (Ni), cobalt (Co), tin (Sn), silicon (Si), iron (Fe), antimony (Sb), aluminum (Al), or bismuth (Bi). Method of producing a carbon fiber, characterized in that the salt or organometallic compound containing any one or more selected metals. The method of claim 3, wherein
The polyperfuryl alcohol: the weight ratio of the carbon precursor is 1: method of producing carbon fibers, characterized in that from 100 to 100. The method of claim 3, wherein
The polyperfuryl alcohol: the weight ratio of the polymer resin is 1: method of producing a carbon fiber, characterized in that 20. The method of claim 1,
The spinning composition: the weight ratio of the metal precursor is 1: method for producing carbon fiber, characterized in that from 0.015 to 0.5. Carbon fiber produced by the manufacturing method according to claim 1. An electrode material for a lithium secondary battery or a solar cell comprising the carbon fiber of claim 14.

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