KR100936488B1 - Carbon Nanofiber Comprising Vanadium Catalyst Treated Fluorine as a Hydrogen Storage Medium and Manufacturing Method Thereof - Google Patents

Abstract

The present invention relates to a carbon nanofiber for a hydrogen storage medium containing a fluorine-treated vanadium catalyst and a method of manufacturing the same.

Method for producing a carbon nanofiber for hydrogen storage medium containing a fluorine-treated vanadium catalyst according to the present invention comprises the steps of (1) mixing a polymer precursor, vanadium oxide and a solvent; (2) electrospinning the mixture of step (1) to produce nanofibers containing vanadium oxide; (3) oxidizing for stabilization of the electrospun nanofibers containing vanadium oxide prepared in step (2); (4) Oxide radicals generated by thermally decomposing the electrospun nanofibers and thermally decomposing vanadium oxides by heat-treating the electrospun nanofibers containing vanadium oxide stabilized through the process of 'step (3)'. Combining with carbon to form pores of the microstructure while being removed with carbon monoxide and carbon dioxide; (5) activating by adding potassium hydroxide solution to carbon nanofibers containing a vanadium catalyst having pores of fine structure through the process of 'step (4)'; (6) fluorination of the carbon nanofibers containing the activated vanadium catalyst through the process of step (5).

According to the present invention, the vanadium catalyst is uniformly present inside and outside of the carbon nanofibers and is connected to the pores of the microstructure, ie vanadium and the large difference in electronegativity due to the action of the fluorine functional groups. Due to the catalytic role of fluorine, the hydrogen storage capacity of carbon nanofibers can be significantly increased.

Hydrogen, hydrogen storage, vanadium, fluorine, catalyst, carbon nanofiber

Description

Carbon Nanofiber Comprising Vanadium Catalyst Treated Fluorine as a Hydrogen Storage Medium and Manufacturing Method Thereof}

The present invention relates to a carbon nanofiber for a hydrogen storage medium containing a fluorine-treated vanadium catalyst and a method for manufacturing the same, and more particularly, to form nanofibers containing vanadium oxide through electrospinning, and to heat treatment The present invention relates to a carbon nanofiber for a hydrogen storage medium containing a fluorinated vanadium catalyst having an improved hydrogen storage capability by removing oxides, forming pores of fine structure, and finally performing fluorine treatment, and a method of manufacturing the same.

With the recent surge in international crude oil prices, attention has been focused on hydrogen energy as a promising field for alternative energy sources. In particular, in Korea, where most of its energy sources depend on foreign countries, alternative energy development has emerged as a proposition that affects the life and death of a country.

Hydrogen energy is pollution-free clean energy generated by using water, and is an alternative energy to fossil fuels such as petroleum, and energy using water as an infinite resource. In addition, when the carbon dioxide emission of coal is 100 as a unit energy product standard, petroleum and natural gas emit 80 and 60 carbon dioxide, respectively, while hydrogen does not emit any carbon dioxide, which is an environmentally friendly energy resource. There is no fear of resource exhaustion. Hydrogen energy can be used in almost all fields used in current energy systems such as general fuels, hydrogen vehicles, hydrogen airplanes, and fuel cells.

However, commercialization of hydrogen as energy requires a highly efficient hydrogen storage medium. To date, as a method of storing hydrogen, a liquefied hydrogen storage method, a high pressure hydrogen storage method, and a hydrogen storage method using a solid material are known. The liquefied hydrogen storage method has a disadvantage in that a large cost is required to maintain the storage container at a temperature below the liquefaction point of hydrogen, and the high pressure hydrogen storage method has a problem in the development and stability of a lightweight hydrogen storage container that can withstand high pressure.

Therefore, many hydrogen storage methods using solid materials, especially alloys and carbon materials, have been studied, but the hydrogen storage capacity for commercialization has not been met. Recently, research on metal / carbon composites having both the advantages of alloys and carbon materials has been actively conducted. Most of the metal / carbon composites produced as a hydrogen storage medium have two major disadvantages. That is, when the metal catalyst is used by the doping and impregnation methods, the metal catalyst exists only outside the carbon material, so the hydrogen storage efficiency of the metal catalyst cannot be improved in the pores inside the carbon, and the metal catalyst and the carbon precursor are not expected. When the composite is prepared by mixing the metal catalyst in the carbon material is difficult to be connected to the pores, it is difficult to act as a catalyst to increase the hydrogen storage capacity due to the pore structure inside the carbon material, hydrogen storage efficiency by the metal catalyst The increase in was bound to be lowered.

The present invention has been made in order to solve the above problems, to form a nanofiber containing vanadium oxide through the electrospinning, and heat treatment thereon to remove the oxide and at the same time to form pores of the microstructure, and finally fluorine Through the treatment, the vanadium catalyst is present evenly inside and outside of the carbon nanofibers and is connected to the pores of the microstructure, and the fluorine-treated vanadium catalyst which can greatly increase the hydrogen storage capacity by the fluorine functional group imparted. An object of the present invention is to provide a carbon nanofiber for hydrogen storage medium and a method for producing the same.

The present invention provides a carbon nanofiber for a hydrogen storage medium containing a fluorine-treated vanadium catalyst and a method for producing the carbon nanofiber, according to the present invention,

(1) mixing a polymer precursor, vanadium oxide and a solvent;

(2) electrospinning the mixture of step (1) to produce nanofibers containing vanadium oxide;

(3) oxidizing for stabilization of the electrospun nanofibers containing vanadium oxide prepared in step (2);

(4) Oxide radicals generated by thermally decomposing the electrospun nanofibers and thermally decomposing vanadium oxides by heat-treating the electrospun nanofibers containing vanadium oxide stabilized through the process of 'step (3)'. Combining with carbon to form pores of the microstructure while being removed with carbon monoxide and carbon dioxide;

(5) activating by adding potassium hydroxide solution to carbon nanofibers containing a vanadium catalyst having pores of fine structure through the process of 'step (4)';

(6) fluorination of the carbon nanofibers containing the activated vanadium catalyst through the process of step (5).

The mixing ratio of the polymer precursor and vanadium oxide in the step (1) is preferably from 99 to 20: 1 to 80 wt%, more preferably from 90 to 70:10 to 30 wt%.

The polymer precursor of 'step (1)' is composed of petroleum pitch, coal pitch, polyimide, polybenzimidazole, polyacrylonitrile, mesophase pitch, furryl alcohol, phenol, cellulose, sucrose and polyvinyl chloride It is preferably selected from the group.

The step of oxidizing the 'step (3)' is heated at a rate of 1 to 5 ℃ / min, it is preferably made for 5 to 10 hours in the temperature range of 200 to 300 ℃.

The heat treatment step of the 'step (4) is made at a temperature of 690 ℃ or more melting point of vanadium oxide.

In particular, the heat treatment step of the 'step (4)' is preferably heated to a rate of 5 to 10 ℃ / min, and finally made for 0.5 to 5 hours in the temperature range of 800 to 1,200 ℃.

The step of activating the 'step (5)' is carried out using a potassium hydroxide solution.

It is preferable that it is 2-10 M, and, as for the density | concentration of the said potassium hydroxide solution, it is more preferable that it is 6-8 M.

The fluorine treatment in step (6) is performed using a mixed gas of fluorine and an inert gas.

It is preferable that the mixing ratio of the fluorine and the inert gas is 5 to 95: 95 to 5 vol%, and more preferably 10 to 20: 90 janny 80 vol%.

The pressure of the mixed gas of the fluorine and the inert gas is preferably 0.1 to 5 atmospheres, more preferably 0.5 to 2 atmospheres.

The inert gas is preferably nitrogen, argon or helium.

The present invention also provides a carbon nanofiber for hydrogen storage medium containing a fluorine-treated vanadium catalyst prepared by the method for producing a carbon nanofiber for hydrogen storage medium containing the fluorine-treated vanadium catalyst described above.

According to the present invention, the vanadium catalyst is uniformly present inside and outside of the carbon nanofibers and is connected to the pores of the microstructure, ie vanadium and the large difference in electronegativity due to the action of the fluorine functional groups. Due to the catalytic role of fluorine, the hydrogen storage capacity of carbon nanofibers can be significantly increased.

The present invention provides a method for producing carbon nanofibers for hydrogen storage medium containing a fluorine-treated vanadium catalyst, the method for producing carbon nanofibers for hydrogen storage medium according to the present invention,

(1) mixing a polymer precursor, vanadium oxide and a solvent;

(2) electrospinning the mixture of step (1) to produce nanofibers containing vanadium oxide;

(3) oxidizing for stabilization of the electrospun nanofibers containing vanadium oxide prepared in step (2);

(4) Oxide radicals generated by thermally decomposing the electrospun nanofibers and thermally decomposing vanadium oxides by heat-treating the electrospun nanofibers containing vanadium oxide stabilized through the process of 'step (3)'. Combining with carbon to form pores of the microstructure while being removed with carbon monoxide and carbon dioxide;

(5) activating by adding potassium hydroxide solution to carbon nanofibers containing a vanadium catalyst having pores of fine structure through the process of 'step (4)';

(6) fluorination of the carbon nanofibers containing the activated vanadium catalyst through the process of step (5).

The mixing ratio of the polymer precursor and vanadium oxide in the step (1) is preferably from 99 to 20: 1 to 80 wt%, more preferably from 90 to 70:10 to 30 wt%.

When the mixing ratio of the polymer precursor and vanadium oxide is out of the range of 99 to 20: 1 to 80 wt%, there is a problem in that the formation of carbon nanofibers is poor.

The polymer precursor of 'step (1)' is composed of petroleum pitch, coal pitch, polyimide, polybenzimidazole, polyacrylonitrile, mesophase pitch, furryl alcohol, phenol, cellulose, sucrose and polyvinyl chloride It is preferably selected from the group.

The solvent used in the 'step (1)' may be any solvent as long as it dissolves the polymer precursor. For example, an organic solvent such as dimethylformaldehyde, N-methylpyrrolidone tetrahydrofuran, chloroform, or the like may be used. Or water may be used.

The step of oxidizing the 'step (3)' is heated at a rate of 1 to 5 ℃ / min, it is preferably made for 5 to 10 hours in the temperature range of 200 to 300 ℃.

In the oxidizing step, when the temperature increase rate is slower than 1 ° C./min, nitrogen is included in the polymer precursor in the oxidation process due to a slow reaction rate, and a cyclization reaction occurs by reacting oxygen and carbon. It will not lose, and it will also lower the fiber yield.

If the temperature increase rate is faster than 5 ℃ / min, the stabilization of the island is unstable due to the fast reaction rate, the electrospinning nanofiber melts or becomes glass transition during the next heat treatment (carbonization), so that the fiber shape cannot be maintained. do.

Finally, if the oxidizing temperature is lower than 200 ° C, the oxidation reaction is incomplete, and during the next heat treatment (carbonization), the electrospun nanofibers melt or become glass transition, and thus the fiber shape cannot be maintained. It doesn't work out smoothly.

When the oxidation temperature is higher than 300 ° C., a high rate of oxidation causes a rapid reaction, and thus the cyclization reaction is not performed smoothly due to the carbon-oxygen coupling reaction in the peroxygen state.

When the oxidation time is shorter than 5 hours, the same phenomenon occurs as when the final oxidation temperature is lower than 200 ° C., and when the oxidation time is longer than 10 hours, it is different from the case where the oxidation time is 10 hours. No unwanted reactions occur.

The heat treatment step of the 'step (4) is made at a temperature of 690 ℃ or more melting point of vanadium oxide.

In particular, the heat treatment step of the 'step (4)' is heated to a rate of 5 to 10 ℃ / min, it is preferably made for 0.5 to 5 hours in the temperature range of 800 to 1,200 ℃ finally.

When the temperature increase rate is lower than 5 ° C / min in the heat treatment step and the final heat treatment at a temperature higher than 1,200 ° C has a disadvantage in that the reaction time increases and energy consumption increases. When the temperature increase rate is faster than 10 ℃ / min there is a problem that a lot of volatilization is lowered the yield of carbon nanofibers. In addition, when the final heat treatment is performed at a temperature lower than 800 ° C., there is a possibility that pyrolysis of vanadium oxide is not completed.

When the heat treatment time is shorter than 0.5 hours, the thermal decomposition of vanadium oxide is not sufficiently performed, and when the heat treatment time is longer than 5 hours, there is no difference from the case where the heat treatment time is 5 hours, and an unnecessary reaction occurs.

The step of activating the 'step (5)' is carried out using a potassium hydroxide solution.

It is preferable that it is 2-10 M, and, as for the density | concentration of the said potassium hydroxide solution, it is more preferable that it is 6-8 M.

This is because when the concentration of the potassium hydroxide solution is lower than 2 M, activation is not sufficiently achieved, and there is no significant difference from the case of 10 M higher than 10 M.

The fluorine treatment in step (6) is performed using a mixed gas of fluorine and an inert gas.

The mixing ratio of the fluorine and the inert gas is preferably 5 to 95: 95 to 5 vol%, more preferably 10 to 20: 90 to 80 vol%.

The pressure of the mixed gas of the fluorine and the inert gas is preferably 0.1 to 5 atmospheres, more preferably 0.5 to 2 atmospheres.

When the mixing ratio of the fluorine is lower than 5 vol% or the pressure of the mixed gas of the fluorine and the inert gas is lower than 0.1 atm, the amount of fluorine is too small compared to the vanadium catalyst, so that the effect of fluorine treatment, that is, the vanadium catalyst-carbon nanofiber- It is hard to expect the improvement of hydrogen storage capacity by fluorine. If the mixing ratio of fluorine is higher than 95 vol% or the pressure of the mixed gas of fluorine and inert gas is higher than 5 atm, the difference in electronegativity is caused by perfluorination. It is difficult to expect much improvement of hydrogen storage capacity by principle.

The inert gas is preferably nitrogen, argon or helium.

The present invention also provides a carbon nanofiber for hydrogen storage medium containing a fluorine-treated vanadium catalyst prepared by the method for producing a carbon nanofiber for hydrogen storage medium containing the fluorine-treated vanadium catalyst described above.

Carbon nanofibers for hydrogen storage medium containing a fluorine-treated vanadium catalyst prepared by the present invention is a fluorine functional group provided with the vanadium catalyst is connected to the pores of the microstructure while being present inside and outside the carbon nanofibers. By the action of hydrogen storage capacity can be significantly increased.

That is, fluorine is relatively negative due to the difference in electronegativity between fluorine and vanadium catalyst (fluorine: 4.0, vanadium: 1.6), and electrons of hydrogen molecules are concentrated on either side in this region as the vanadium catalyst is positive. This will happen. Due to this phenomenon, the portion of the electrons concentrated in the hydrogen molecule is negatively affected by the vanadium catalyst, which is relatively positive, and into the pores of the carbon material. Under the influence of negative fluorine catalysts, hydrogen molecules are stored in the pores of carbon nanofibers.

Hereinafter, the present invention will be described in more detail with reference to Examples.

Example

For hydrogen storage media containing fluorinated vanadium catalyst Carbon nanofiber  Produce

Polyacrylonitrile was dissolved in dimethylformaldehyde to prepare a polyacrylonitrile solution. To this solution, vanadium oxide was added as a catalyst material for improving hydrogen storage capacity. The composition ratio of each component is as follows.

 Nanofibers were prepared by electrospinning the mixture.

 A schematic diagram of the device used for electrospinning is shown in FIG. 1.

The conditions of the electrospinning were a voltage of 15 kV, a distance between the collector and the syringe tip (TCD) of 15 cm, a syringe pump flow rate of 1.0 ml / h, and a collector speed of 200 rpm.

In order to stabilize the nanofibers containing the electrospun vanadium oxide, the temperature was raised at a rate of 3 ° C./min and finally oxidized at 250 ° C. for 8 hours.

The nanofibers containing the electrospun vanadium oxide subjected to the oxidation process were heated at a rate of 7 ° C./min and finally heat treated at 1,050 ° C. for 1 hour. Nitrogen gas was injected into the inert gas at a rate of 20 cc / min during the heat treatment.

Through the heat treatment process as described above, the carbon nanofibers containing the vanadium catalyst in which the pores of the microstructures were formed were evenly sprayed with 5 M per 1g of carbon hydroxide solution to activate the carbon nanofibers. Activation was carried out at 750 ° C. for 3 hours.

The fluorine treatment was performed on the carbon nanofibers containing the vanadium catalyst activated by the above procedure. The schematic diagram of the apparatus for fluorine treatment is shown in FIG.

The fluorine treatment was performed using a mixed gas in which fluorine gas and argon gas were mixed at 20:80 vol%. It carried out for 30 minutes at 1 atmosphere and room temperature using the mixed gas.

Carbon nanofibers for hydrogen storage medium containing the fluorine-treated vanadium catalyst through the above process was obtained.

Performance test

3 is an XPS analysis result of carbon nanofibers for hydrogen storage medium containing a fluorine-treated vanadium catalyst according to the present embodiment. The vanadium catalyst is present in the carbon nanofibers through the above results, and it can be confirmed that the surface of the carbon nanofibers is modified by the fluorine treatment.

The measurement results of the specific surface area of the carbon nanofibers according to the present embodiment are shown in FIG. 4. Carbon nanofibers according to this embodiment had a specific surface area of 2,800 m 2 / g, of which the surface area by micropores was about 18% of the total specific surface area.

Finally, the hydrogen storage capacity of the carbon nanofibers according to the present example was evaluated. The schematic diagram of the apparatus for evaluating a hydrogen storage capacity is shown in FIG. Prior to evaluating the hydrogen storage capacity, pretreatment was performed to evaporate water at 150 ° C. for 1 hour. Hydrogen storage capacity was measured in the range of 0 to 100 atm at a constant temperature of 30 ℃, the results are shown in FIG. The hydrogen storage capacity of this example was about 3.1 wt%.

Comparative example  1: for hydrogen storage medium containing vanadium catalyst Carbon nanofiber  Manufacturing and performance test

In the above embodiment, carbon nanofibers for a hydrogen storage medium containing a vanadium catalyst were manufactured in a manner that fluorine treatment was omitted.

7 is an XPS analysis result of carbon nanofibers according to Comparative Example 1. Through the results it was confirmed that the vanadium catalyst is present in the carbon nanofibers.

The specific surface area characteristics of the carbon nanofibers according to Comparative Example 1 were analyzed and their measurement results are shown in FIG. 4. Carbon nanofibers according to Comparative Example 1 had a specific surface area of 2,900 m 2 / g, of which the surface area by micropores was about 28% of the total specific surface area.

Next, the hydrogen storage capacity was evaluated in the same manner as in the above example, and this is shown in FIG. 6. The hydrogen storage capacity of Comparative Example 1 was about 2.5 wt%.

Comparing the results of the present Comparative Example 1 with the results of the above example, it can be seen that the hydrogen storage capacity was remarkably improved by the fluorine treatment.

Comparative example  2: for hydrogen storage media Carbon nanofiber  Manufacturing and performance test

In the above embodiment, carbon nanofibers for hydrogen storage medium were prepared by omitting the addition of vanadium oxide and fluorine treatment.

8 is an XPS analysis result of carbon nanofibers according to Comparative Example 2. In the carbon nanofibers according to Comparative Example 2, 94% or more is composed of carbon, and other components are composed of trace amounts of nitrogen and oxygen.

The specific surface area characteristics of the carbon nanofibers according to Comparative Example 2 were analyzed and their measurement results are shown in FIG. 4. Carbon nanofibers according to Comparative Example 2 had a specific surface area of 2,600 m 2 / g, of which the surface area by micropores was about 21% of the total specific surface area.

Next, the hydrogen storage capacity was evaluated in the same manner as in the above example, and the results are shown in FIG. 6. The hydrogen storage capacity according to Comparative Example 2 was about 1.8 wt%.

Comparing the results of the present Comparative Example 2 with the results of Examples and Comparative Example 1, it can be seen that the hydrogen storage capacity is significantly improved by the addition of vanadium oxide and fluorine treatment.

Although the present invention has been described with reference to the above-described embodiments and the accompanying drawings, different embodiments may be configured within the concept and scope of the present invention. Therefore, the scope of the present invention is defined by the appended claims and equivalents thereof, and is not limited by the specific embodiments described herein.

Figure 1 shows a schematic diagram of an electrospinning apparatus for producing carbon nanofibers according to an embodiment of the present invention.

<Code description>

1 pump high voltage generator, 2 pump high voltage generator

3 ... binding machine, 4 ... syringe

Figure 2 shows a schematic diagram of a fluorine treatment apparatus for producing carbon nanofibers according to an embodiment of the present invention.

<Code description>

1 ... fluorine gas container 2 ... nitrogen gas container

3 ... oxygen gas container 4 ... temporary storage container

5 ... Sodium fluoride pellets 6 ... Reactor

7 ... pressure gauge 8 ... aluminum trioxide

9 ... glass valve 10 ... liquefied nitrogen

11 ... vacuum pump

Figure 3 shows the XPS data of the carbon nanofibers for hydrogen storage medium containing a fluorine-treated vanadium catalyst according to an embodiment of the present invention.

Figure 4 shows the specific surface area analysis data of Examples, Comparative Example 1 and Comparative Example 2 of the present invention.

5 shows a schematic diagram of an apparatus for measuring hydrogen storage capacity.

<Code description>

S ₁ ... Temporary container 1 S ₂ ... Temporary container 2

T ₁ ... thermometer 1 T ₂ ... thermometer 2

T ₃ ... thermometer 3 P ₁ ... pressure gauge (10 ^-4 torr)

P ₂ ... pressure gauge (20 psia) P ₃ ... pressure gauge (10 atm)

P ₄ ... pressure gauge (100 atm) V ... valve

VP ... Vacuum Pump EV ... Exhaust Valve

Figure 6 shows the measurement of the hydrogen storage capacity of Examples, Comparative Example 1 and Comparative Example 2 of the present invention.

7 shows XPS data of Comparative Example 1. FIG.

8 shows XPS data of Comparative Example 2. FIG.

Claims (15)

(1) mixing a polymer precursor, vanadium oxide and a solvent; (2) electrospinning the mixture of step (1) to produce nanofibers containing vanadium oxide; (3) oxidizing for stabilization of the electrospun nanofibers containing vanadium oxide prepared in step (2); (4) Oxide radicals generated by thermally decomposing the electrospun nanofibers and thermally decomposing vanadium oxides by heat-treating the electrospun nanofibers containing vanadium oxide stabilized through the process of 'step (3)'. Combining with carbon to form pores of the microstructure while being removed with carbon monoxide and carbon dioxide; (5) activating by adding potassium hydroxide solution to carbon nanofibers containing a vanadium catalyst having pores of fine structure through the process of 'step (4)'; (6) carbon for a hydrogen storage medium containing a fluorine-treated vanadium catalyst comprising the step of fluorination of the carbon nanofibers containing the activated vanadium catalyst through the process of 'step (5)' Method for producing nanofibers. The method of claim 1, Method for producing a carbon nanofibers for hydrogen storage medium containing a fluorinated vanadium catalyst, characterized in that the mixing ratio of the polymer precursor and vanadium oxide of the 'step (1)' is 99 to 20: 1 to 80 wt%. The method of claim 2, Method for producing a carbon nanofibers for hydrogen storage medium containing a fluorine-treated vanadium catalyst, characterized in that the mixing ratio of the polymer precursor and vanadium oxide of the 'step (1)' is 90 to 70: 10 to 30 wt%. The method of claim 1, The polymer precursor of 'step (1)' is composed of petroleum pitch, coal pitch, polyimide, polybenzimidazole, polyacrylonitrile, mesophase pitch, furfuryl alcohol, phenol, cellulose, sucrose and polyvinyl chloride A method for producing carbon nanofibers for a hydrogen storage medium containing a fluorine-treated vanadium catalyst, characterized in that selected from the group consisting of. The method of claim 1, The step of oxidizing the 'step (3)' is a fluorine-treated vanadium catalyst, characterized in that the temperature is raised at a rate of 1 to 5 ℃ / min, and finally for 5 to 10 hours in the temperature range of 200 to 300 ℃ Method for producing carbon nanofibers for hydrogen storage medium containing. The method of claim 1, The heat treatment step of the 'step (4)' is a method for producing carbon nanofibers for hydrogen storage medium containing a fluorine-treated vanadium catalyst, characterized in that at a temperature of 690 ℃ or more melting point of vanadium oxide. The method of claim 1, The heat treatment step of the 'step (4)' is heated to a rate of 5 to 10 ℃ / min, and finally contains a fluorine-treated vanadium catalyst, characterized in that made for 0.5 to 5 hours in the temperature range of 800 to 1,200 ℃ Method for producing carbon nanofibers for hydrogen storage medium. The method of claim 1, The method of producing carbon nanofibers for hydrogen storage medium containing a fluorinated vanadium catalyst, characterized in that the concentration of the potassium hydroxide solution in the step of activating the 'step (5)' is 2 to 10M. The method of claim 8, The concentration of the potassium hydroxide solution is a method of producing carbon nanofibers for hydrogen storage medium containing a fluorine-treated vanadium catalyst, characterized in that 6 to 8 M. The method of claim 1, The step of treating fluorine in the 'step (6)' is made using a mixed gas of fluorine and an inert gas, The mixing ratio of the fluorine and inert gas is 5 to 95: 95 to 5 vol% method for producing carbon nanofibers for hydrogen storage medium containing a fluorine-treated vanadium catalyst, characterized in that. The method of claim 10, The mixing ratio of the fluorine and the inert gas is 10 to 20: 90 to 80 vol%, characterized in that the manufacturing method of carbon nano island oil for hydrogen storage medium containing a fluorine-treated vanadium catalyst. The method of claim 10, The pressure of the mixed gas of the fluorine and inert gas is 0.1 to 5 atm pressure method of producing carbon nanofibers for hydrogen storage medium containing a fluorine-treated vanadium catalyst. The method of claim 12, The pressure of the mixed gas of the fluorine and inert gas is a method of producing carbon nanofibers for hydrogen storage medium containing a fluorine-treated vanadium catalyst, characterized in that 0.5 to 2 atm. The method of claim 10, The inert gas is a method for producing carbon nanofibers for hydrogen storage medium containing a fluorine-treated vanadium catalyst, characterized in that nitrogen, argon or helium. A carbon nanofiber for a hydrogen storage medium containing a fluorinated vanadium catalyst prepared by a method for producing a carbon nanofiber for a hydrogen storage medium containing the fluorinated vanadium catalyst according to any one of claims 1 to 14.

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