KR100513209B1 - Supercapacitor and methods for manufacturing Ruthenium Oxide and Electrode used in the Supercapacitor - Google Patents

Abstract

The invention ruthenium chloride _{(RuCl 3 · n H 2 O} ) from the amorphous ruthenium oxide _{(RuO 2 · n H 2 O} ) a process for producing and a method for producing an electrode for a supercapacitor using an amorphous ruthenium oxide and the electrode It provides a supercapacitor comprising a. Amorphous ruthenium oxide The material is prepared from ruthenium chloride by synthesis, washing and heat treatment using an aqueous alkali solution such as sodium hydroxide. The amorphous ruthenium oxide is obtained at a temperature of 150 ° C. or less, and a supercapacitor is constructed using ruthenium oxide prepared at a temperature of 150 ° C. or less. Ruthenium oxide electrode is made of polymer binder such as polyvinylidene fluoride (PVDF), conductive material of vapor-grown carbon fiber (including carbon nanotube) and super p. Black (carbon black), and current collector of tantalum The supercapacitor is constructed using the prepared electrode, the separator of Celgard 3501, and an electrolyte solution of an aqueous sulfuric acid solution of 5 mol or less.

Description

Supercapacitors and methods for manufacturing Ruthenium Oxide and Electrode used in the Supercapacitor}

The present invention relates to a supercapacitor, and more particularly, to a supercapacitor, a rudennium oxide and an electrode used in the supercapacitor.

As the information society enters, portable information devices such as mobile phones, laptops, camcorders, PDAs, etc. are also becoming smaller and multifunctional, and energy sources, which are core devices, also require high output characteristics. In the case of a battery, there is a problem in that the life is shortened due to the use of high power. The miniaturization and long life of the energy source can be realized by hybridizing a high power density supercapacitor and a high energy secondary battery. To this end, it is necessary to develop a high power density supercapacitor technology for a hybrid power supply. Supercapacitors can be classified into activated carbon-based, conductive polymer-based, and metal oxide-based capacitors, depending on the electrode material. Activated carbon-based supercapacitors have been commercialized for low-current type memory backup, and recently, they are attempting to be applied to the use of secondary batteries by improving energy density and power density characteristics. Although the conductive polymer is partially used as an electrolyte for capacitors, there is a problem of life due to deterioration as an electrode material. Metal oxide-based supercapacitors exhibit excellent output characteristics.

The electric double layer capacitor has a higher power density characteristic than a conventional secondary battery because it stores energy by adsorption of electrolyte ions in the electric double layer existing between the electrode and the electrolyte, and uses a porous activated carbon electrode having a large specific surface area. Better energy density than capacitor

Electrochemical capacitors are very important as auxiliary energy storage devices in hybrid electric devices powered by rechargeable batteries. Electrochemical double layer capacitors (EDLC) utilize physical separation of electronic charges from electrodes and electrolyte ions adsorbed on their surfaces. Bilayer capacitors have a lower specific capacitance than virtual supercapacitors by paradeik reactions. When activated carbon is used as an electrode material and an aqueous electrolyte solution of potassium hydroxide is used, the specific capacitance is known to be about 300 F / g.

Supercapacitors of metal oxide electrodes using virtual capacitance (psuedo-capacitance) have a higher specific capacitance than double layer capacitors because they show an accumulation mechanism in which protons move to oxidation and reduction of metal oxides. Development of an electrode material of cobalt oxide and manganese oxide is in progress, and the specific capacitances of the cobalt oxide and manganese oxide electrode materials are about 450 F / g and 340 F / g, respectively.

Conventional ruthenium oxide supercapacitors have a low specific capacitance using a crystalline material and high electrode resistance due to the use of a single conductive material.

Conventionally, electrode materials such as cobalt oxide and manganese oxide used in supercapacitors have disadvantages of low specific capacitance and large resistance.

Conventional capacitors have used particulate conductive materials, and mainly carbon black based conductive materials. The particulate conductive material has excellent conductivity characteristics in itself, but a conductive path is formed by contact between the particles. Because of the continuous contact resistance between the particles, the overall resistance is equivalent to the series connection of the resistors, resulting in a higher resistance value.

The present invention has been made to solve these disadvantages, and to provide a supercapacitor applying a ruthenium oxide material having a high specific capacitance.

The present invention seeks to provide a supercapacitor with optimized manufacturing conditions to have a higher specific capacitance by optimizing the manufacturing conditions of a high specific capacitance ruthenium oxide material.

The present invention provides a ruthenium oxide supercapacitor having high specific capacitance and excellent conductivity.

The present invention is to develop a supercapacitor having a high capacitance from ruthenium chloride hydrate, and to improve the conductive material to provide a supercapacitor having excellent conductivity.

In the present invention, the ruthenium oxide hydrate material is chemically reacted with an aqueous alkali solution such as sodium hydroxide from ruthenium chloride hydrate to obtain a ruthenium oxide precursor and heat-treating it at an appropriate temperature and time to provide a high specific capacitance amorphous ruthenium oxide.

In order to invent the above-described amorphous ruthenium oxide from the electrode material, a superconductor electrode having a high conductivity is used together with a particulate conductive material such as carbon black together with a vapor-grown carbon fiber or nanotube material which is a fibrous conductive material. Compared with the electrode composed of the conductive material or the fibrous conductive material alone, an electrode having a better electron conduction path is manufactured, and as a result, the equivalent resistance of the supercapacitor is reduced to improve the output characteristics of the supercapacitor.

The present invention is to provide a supercapacitor having improved resistance characteristics by optimizing the concentration of sulfuric acid electrolyte as another method for reducing the equivalent resistance of the supercapacitor.

To this end, in the present invention, an amorphous ruthenium oxide material is synthesized from ruthenium chloride using sodium hydroxide (NaOH), synthesized, washed, and heat treated. The ruthenium oxide (RuO ₂ ) electrode uses a combination of polyvinylidene fluoride (PVDF), a conductive material of vapor-grown carbon fiber (VGCF) and super p. Black, and a current collector of tantalum (Ta). The supercapacitor is prepared by using a separator of Celgard 3501 and an electrolyte solution of sulfuric acid solution of 5 mol or less. The complete amorphous ruthenium oxide was obtained upon heat treatment at 130 ° C., and the supercapacitor prepared therefrom had a high specific capacitance of 556 F / g-RuO ₂ · nH ₂ O and 0.664 mΩ · cm [AC] for the saturated carmel reference electrode potential. AC impedance, 1 kHz frequency, low equivalent resistance (ESR) is obtained.

Hereinafter, a ruthenium oxide electrode for a supercapacitor according to a preferred embodiment of the present invention, a supercapacitor having such a ruthenium oxide, and a method of manufacturing such a ruthenium oxide supercapacitor will be described with reference to the accompanying drawings.

Metal oxide-based supercapacitors using a virtual capacitance utilize a Paradaic reaction in an electrode, and characteristics studies using a ruthenium oxide electrode have been made. The reactor of the virtual capacitance is the same as the formulas (1) and (2) in the anode and cathode, respectively. Therefore, the overall reaction is the same as Has a value between 0 and 1.

As can be seen in the reaction scheme, there is no change in the concentration of the electrolyte salt during the charging and discharging process, and it can be seen that proton transfer occurs between the positive electrode and the negative electrode.

According to the use of the particulate conductive and fibrous composite conductive materials, it is possible to produce electrodes and supercapacitors having better conductivity. The fibrous conductive material, when viewed in the form of microelectrode, connects the medium-distance conductive path with a single fiber or tube, so that the conductive material exhibits higher conductivity than providing the conductive path through the multi-phase contact. Can be. In the case of using the fibrous conductive material alone, the conductive path characteristics of the medium distance are excellent, but the short-range electron conduction paths to the particles of each electrode material are not smooth, so that the electrode alone exhibits high electrode resistance. The particulate conductive material alone also exhibits low conductivity by forming a conductive path through connection by contact. In this concept, it is more effective to use particulate and fibrous composite conductive materials.

<Example 1>

According to the reaction scheme of FIG. 1, an amorphous ruthenium oxide powder was synthesized by a sol-gel method, and an electrode was manufactured, and a supercapacitor was prepared using the same.

A solution was prepared by dissolving ruthenium chloride in distilled water and reacting by slowly dropwise addition of sodium hydroxide solution. When the loss of solution (pH) reaches 7, the dropwise addition is stopped, and filtered through a glass filter to prepare a black ruthenium oxide powder. The washing process of dispersing the prepared black powder in distilled water, stirring and filtration is repeated several times. The specific surface area of the material before the heat treatment was 90.58 ± 0.25 m ² / g by the BET method, the thermal analysis was carried out using the material at a scanning rate of 5 ℃ / min, the results are shown in FIG. The washed ruthenium oxide powder was heat-treated at 130 ° C. to produce an amorphous ruthenium oxide.

An electrode of 2 × 2 cm ² was prepared using an amorphous ruthenium oxide prepared by heat treatment at 130 ° C. Detailed manufacturing process is to completely dissolve polyvinylidene fluoride in N-Methyl-2-pyrrolidone (N-Methyl-2-pyrrolidone) solvent, add super p black and ultrasonic dispersion for 30 minutes , Vapor-grown carbon fiber and amorphous ruthenium oxide were added, and stirred together with a zirconia ball to prepare an electrode mixture.

Figure 3 shows the results of the particle size distribution analysis according to the ultrasonic dispersion of the superpi black, the original superpi black has a maximum particle size distribution at 60 ~ 70 micrometers, but the superpi black after ultrasonic dispersion for 30 minutes or 60 minutes is 10 It can be seen that the particle size was reduced to micrometers and dispersed into 0.3 micrometer microparticles, and the 30 minute and 60 minute particle size distribution did not change, so that 30 minutes of ultrasonic dispersion conditions were used.

Figure 4 shows an electron scanning micrograph of the original superpi black and superpi black ultrasonically dispersed for 30 minutes. An electron scanning microscope photograph of the vapor-grown carbon fiber is shown in FIG. 5, and FIG. 6 shows an electron scanning microscope photograph of the amorphous ruthenium oxide prepared by heat treatment at 130 ° C. FIG.

FIG. 7 shows the particle size analysis results of the prepared electrode mixture together with the particle size distribution of superpi black, vapor-grown carbon fiber, and amorphous ruthenium oxide material dispersed by ultrasonic wave for 30 minutes. The particle size of the electrode mixture showed a particle size distribution peak at 6 to 7 and 0.3 micrometers. The mixing ratio is ruthenium oxide: polyvinylidene fluorine: superpi black: vapor phase grown carbon fiber = 84: 10: 3: 3 (weight ratio). After mixing, the dissolved air in the mixture is removed under vacuum, applied to a tantalum current collector, and dried in a dryer at 100 ° C. for 2 hours. The electrode is cut into 2 × 2 cm ² and heated and compressed at 110 ° C. Scanning electron micrographs of the electrodes prepared by heating and pressing are shown in FIG. 8, and the presence of vapor-grown carbon fibers can be confirmed in the photographs.

The ruthenium oxide electrode thus prepared was prepared using a platinum plate counter electrode, a sulfuric acid electrolyte of 5 mol or less, and a saturated caramel reference electrode, and a cyclic potential current method was used for a potential range of -0.15 to 1.15 V (saturated caro Mel reference electrode) was tested at a scanning rate of 2 mV / sec, the results were obtained as shown in Figure 9, the specific capacitance was 538F / g- ruthenium oxide. Hydrolysis reactions were observed at the electrode during the test and showed high specific capacitance at high potential rather than low potential. In the cyclic potential current method, the potential ranges of 0.0 to 1.0 and 0.1 to 1.1 V (based on saturated caramel reference electrode) were tested at a scanning rate of 2 mV / sec, respectively. The specific capacitances were 521 and 556 F / g- ruthenium oxides, respectively. No hydrolysis reaction could be observed at the electrode during the test in these sections.

The supercapacitor assembly was a supercapacitor assembly using two electrodes and Celgard 3501 separator. The assembled supercapacitor was manufactured using the electrolyte solution of sulfuric acid electrolyte solution of 5 mol or less. The prepared supercapacitors were supercapacitors electrochemically prototyped. Electrochemical protonation was performed on the basis of the saturated caramel reference electrode, and was protonated to 0.5 V at an open circuit potential of 0.82 V immediately after assembly. Supercapacitors prototyped at a level of 0.5 V were subjected to constant current charge and discharge tests with current densities of 1, 2, 3, 4, and 5 mA / cm ² at potential ranges of 0 to 1 V, followed by alternating current impedance tests. The first charge / discharge test was performed at a current density of 1 mA / cm ² , and the potential change of the present process is shown in FIG. 12. The charge and discharge current efficiency of the first cycle was 84.8%, after which it was about 89.7%. In the constant current charge / discharge test, specific capacitance results of 151, 144, 142, 139, and 137F / g- ruthenium oxides were obtained according to the current densities 1, 2, 3, 4, and 5 mA / cm ² . Equivalent resistance was 309 mΩ (12 msec) and specific equivalent resistance was 1.236Ω · cm ² .

In the state of discharging this supercapacitor, the equivalent resistance was measured to the frequency range 100kHz-2.5mHz by the AC impedance method. The results are shown in FIG. 13, and the equivalent resistance at 1 kHz was 166 mΩ, the specific equivalent resistance was 0.664Ω · cm ² , and the real part when the imaginary part was 0 was also 166mΩ (0.664Ω · cm ² ).

<Example 2>

An electrode was prepared using a ruthenium oxide material prepared by heat treatment at 140 ° C. by the method of Example 1. A half cell was prepared in the same manner as in Example 1 using the prepared 2x2 cm ² ruthenium oxide electrode, and a scanning speed of 2 mV / was measured in a potential range of 0.0 to 1.0 V (based on saturated caramel reference electrode) by cyclic potential current method. The specific capacitance was 448F / g- ruthenium oxide as shown in FIG. 14.

<Example 3>

An electrode was prepared using a ruthenium oxide material prepared by heat treatment at 150 ° C. by the method of Example 1. A half cell was prepared in the same manner as in Example 1 using the prepared 2x2 cm ² ruthenium oxide electrode, and a scanning speed of 2 mV / was measured in a potential range of 0.0 to 1.0 V (based on saturated caramel reference electrode) by cyclic potential current method. The specific capacitance, tested at sec, was 421F / g- ruthenium oxide and is shown in Figure 17.

<Example 4>

An electrode was prepared using a ruthenium oxide material prepared by heat treatment at 120 ° C. by the method of Example 1. A half cell was prepared in the same manner as in Example 1 using the prepared 2x2 cm ² ruthenium oxide electrode, and a scanning speed of 2 mV / was measured in a potential range of 0.0 to 1.0 V (based on saturated caramel reference electrode) by cyclic potential current method. As a result, the specific capacitance was 405F / g- ruthenium oxide and is shown in FIG. 14.

As shown in Examples 1 to 4, the specific capacitance due to the cyclic potential current curve of the ruthenium oxide material manufactured in the heat treatment temperature range of 120 to 150 ° C is shown in FIG. The highest 521 F / g- ruthenium oxide was obtained on an electrode using an amorphous ruthenium oxide material prepared by heat treatment at 130 ° C.

As a result of phase analysis of the ruthenium oxide material prepared in the heat treatment range of 120 to 150 ° C., an X-ray diffraction pattern as shown in FIG. 15 was obtained. In FIG. 15, the crystalline ruthenium oxide was observed at 130 ° C. or higher, and it was confirmed that amorphous ruthenium oxide was produced at 130 ° C. or lower. Bijeongjeon capacity of the amorphous ruthenium oxide produced by heat treatment at 120 ℃ temperature (405F / g- ruthenate titanium oxide) bijeongjeon capacity of the amorphous ruthenium oxide produced by heat treatment at 130 ℃ temperature than (521F / g- ruthenate titanium oxide) is highly appear. Therefore, only amorphous amorphous ruthenium oxide was formed during ruthenium oxide production, and the highest temperature was found to be 130 ° C.

Example 5

This embodiment shows the difference in characteristics according to the concentration of sulfuric acid electrolyte. The characteristics according to the concentration of the sulfuric acid electrolyte solution were measured by using a 2x2 cm ² electrode, a platinum plate counter electrode, and a saturated caramel reference electrode prepared using an amorphous ruthenium oxide material prepared by heat treatment at 130 ° C. by the method of Example 1. It was tested by cyclic potential current method. The potential range was 0.0 to 1.0 V, the scanning speed was 2 mV / sec, the reference electrode was a saturated caramel electrode, and the specific capacitance of the electrode according to the concentration of sulfuric acid electrolyte was measured. The results are shown in FIG. 16. The concentration of sulfuric acid electrolyte showed the highest specific capacitance at 5M.

Comparative Example 1

In this Comparative Example 1, the conductive material was tested as one type of vapor-grown carbon fiber by the method of Example 1. Electrode composition An electrode was prepared from polyvinylidene fluorine and vapor-grown carbon fiber in the amorphous ruthenium oxide of Example 1 in an N-methylpyrrolidone solvent. The mixing ratio is ruthenium oxide: polyvinylidene fluorine: super pi black: vapor-grown carbon fiber = 84: 10: 0: 6 (weight ratio). The scanning electron micrograph of this electrode is shown in FIG. 17, and the presence of vapor-grown carbon fiber can be confirmed in the photograph. A ² x 2 cm ² electrode of the ruthenium oxide thus prepared was prepared in the same manner as in Example 1, and tested by cyclic potential current method to obtain the result of FIG. 18. The specific capacitance was 394 F / g- ruthenium oxide. Indicated. The supercapacitor assembly was the same as the supercapacitor manufacturing method shown in Example 1 using two electrodes. Supercapacitors prototyped at a level of 0.5 V were subjected to constant current charge and discharge tests with current densities of 1, 2, 3, 4, and 5 mA / cm ² at potential ranges of 0 to 1 V, followed by alternating current impedance tests. The first charge / discharge test was performed at a current density of 1 mA / cm ² , and the potential change of the process is shown in FIG. 19. The charge and discharge current efficiency of the first cycle was 81.7%, after which it was about 89.4%. In the constant current charge / discharge test, specific capacitance results of 126, 117, 112, 108, and 104 F / g- ruthenium oxides were obtained according to the current densities 1, 2, 3, 4, and 5 mA / cm ² . The equivalent resistance at this time was 1,237 mΩ (12 msec) and the specific equivalent resistance was 4.950Ω · cm ² .

In the state of discharging this supercapacitor, the equivalent resistance was measured to the frequency range 100kHz-2.5mHz by the AC impedance method. The results are shown in FIG. 20, and the equivalent resistance at 1 kHz was 680 mΩ and the specific equivalent resistance was 2.723 Ω · cm ² . However, as shown in Fig. 20, the real part when the imaginary part is 0 is also 92mΩ (0.369Ωcm ² ), and the real part is 952mΩ (3.806Ωcm ² ) at the inflection point from (-) to (+). It was.

Comparative Example 2

In Comparative Example 2, the conductive material was tested as one kind of superpi black in the method of Example 1. Amorphous ruthenium oxide, polyvinylidene fluorine, and superpiblack of Example 1 were prepared with an electrode mixture together with 3.5 mL of n-methylpyrrolidone solvent and applied to tantalum foil to prepare an electrode. The mixing ratio is ruthenium oxide: polyvinylidene fluorine: superpi black: vapor phase growth carbon fiber = 84: 10: 6: 0 (weight ratio). The scanning electron micrograph of this electrode is shown in FIG.

The electrode of the thus prepared ruthenium oxide was prepared by the method of Example 1, and tested by cyclic potential current method to obtain the result of FIG. 22, and the specific capacitance was 410 F / g- ruthenium oxide.

Supercapacitor assembly was carried out in the same manner as in Example 1, and was prototyped. Supercapacitors prototyped at a level of 0.5 V were subjected to constant current charge and discharge tests with current densities of 1, 2, 3, 4, and 5 mA / cm ² at potential ranges of 0 to 1 V, followed by alternating current impedance tests. The first charge / discharge test was performed at a current density of 1 mA / cm ² , and the potential change of the present process is shown in FIG. 23. The charge and discharge current efficiency of the first cycle was 81.2%, after which it was about 88.5%. In the constant current charge / discharge test, specific capacitance results of 136, 126, 121, 116, and 111F / g- ruthenium oxide were obtained according to the current densities 1, 2, 3, 4, and 5 mA / cm ² . At this time, the equivalent resistance was 1,107 mΩ (12 msec) and the specific equivalent resistance was 4.427Ω · cm ² .

In the state of discharging this supercapacitor, the equivalent resistance was measured to the frequency range 100kHz-2.5mHz by the AC impedance method. The results are shown in FIG. 24. The equivalent resistance at 1 kHz was 756 mΩ and the specific equivalent resistance was 3.024 Ω · cm ² . However, even when the real part of the imaginary part as shown in Fig. ^{24 0 97mΩ (0.388Ω · cm 2} ) , and the slope is (-) at the inflection point to in () is the real part 1,120mΩ (4.478Ω · cm ² Was.

Comparing Example 1, Comparative Example 1, and Comparative Example 2, it is shown in Table 1, and the mixed ratio ruthenium oxide: polyvinylidene fluorine: superpi black: vapor phase growth carbon fiber = 84: 10: 3: 3 (weight ratio) of the electrode It was confirmed that the properties were superior to those using only superpi black and vapor-grown carbon fiber, respectively, as conductive materials. It was confirmed that the characteristics of the electrode were improved by mixing fibrous vapor-grown carbon fibers with spherical superpi black as shown in FIGS. 8, 17, and 21.

Electrode composition (weight ratio) (ruthenium oxide: polyvinylidene fluorine: super pea black: vapor growth carbon fiber) 84: 10: 3: 3 84: 10: 0: 6 84: 10: 6: 0 Electrode Thickness (micrometer) 70 60 60 Specific capacitance (F / g- ruthenium oxide) Cyclic Potential Current Method (2mV / sec, 0 ~ 1V) 521 394 410 Constant current charge / discharge test current density (1,2,3,4,5 mA / cm ² ) 151, 144, 142, 139, 137 126, 117, 112, 108, 104 136, 126, 121, 116, 111 Equivalent Resistance (mΩ, Ωcm ² ) AC Inductance Law Impedance at 1 kHz 166, 0.664 680, 2.732 756, 3.024 Real part impedance at imaginary part 0 166, 0.664 92, 0.369 97, 0.388 Real part impedance at inflection point from (-) to (+) - 952, 3.806 1120, 4.478 DC impedance method (time = 12 milliseconds) 309, 1.236 1237, 4.950 1107, 4427

Comparative Example 3

Republic of Korea Patent Application No. 10-1999-0039899

In this comparative example, a layered manganese oxide was used in place of the amorphous ruthenium oxide material, and the maximum specific capacitance of 331.4 F / g was shown in Example 8 of the patent.

<Comparative Example 4>

Republic of Korea Patent Application No. 10-1999-0039888

In this comparative example, amorphous manganese oxide was used instead of amorphous ruthenium oxide, and the maximum specific capacitance of 320 F / g was shown in FIG. 6.

Comparative Example 5

Korean Application No. 10-1999-0039898

In this comparative example, amorphous manganese oxide was used in place of the amorphous ruthenium oxide material, and the maximum specific capacitance of 330 F / g was shown in FIG. 4.

On the other hand, the present invention is not limited to the above-described embodiment, but can be carried out by various modifications and variations within the scope not departing from the gist of the present invention, the technical idea that such modifications and variations are also applied to the following claims Should be regarded as belonging to

As described in detail above, the present invention has the following excellent effects.

<Effect 1 of the present invention>

An amorphous ruthenium oxide precursor was synthesized by the development of a sol-gel preparation method using an aqueous sodium hydroxide solution from ruthenium chloride, and the precipitate was washed and heat treated to prepare an amorphous ruthenium oxide.

Effect 2 of the Invention

Heat treatment to produce an amorphous ruthenium oxide, and it was able to produce the electrode shown bijeongjeon a capacity of 521 F / g- ruthenate titanium oxide used as an electrode material for a super-capacitor.

Effect 3 of the Invention

In the case of electrode composition using a superpi black and a gas-grown carbon fiber conductive material, the DC impedance measured at the initial discharge of 12 msec was 1.236Ω · cm ² (309 mΩ), and the value of the superpiblack alone conductive material was 4.427Ω · cm ² Compared with the value of 4.950Ω · cm ² of the gas-phase grown carbon fiber conductive material alone, it showed about 4 times better resistance. This result was also confirmed in the AC impedance, and 0.664 Ωcm ² when the mixed conductive material was used at 1 kHz, the value of the superpi black alone conductive material 3.024Ω · cm ² and the vapor-grown carbon fiber sole conductive material 2.732Ω · Compared with cm ² , it showed 4 times better resistance characteristics.

Effect 4 of the Invention

In the case of an electrode mixed with superpi black and vapor-grown carbon fiber, the specific capacitance is 521 F / g- ruthenium oxide, and the value of superpi black alone conductive material is 410 F / g- ruthenium oxide and vapor-grown carbon fiber. compared to the sole conductive material in the value of 394 F / g- ruthenate titanium oxide exhibited more than 100 F / g- ruthenium oxide high value.

Effect 5 of the Invention

In the case of a supercapacitor using an electrode mixed with superpi black and a conductive material of vapor-grown carbon fiber, the specific capacitance is 151 F / g- ruthenium oxide at a current density of 1 mA / cm ^{2, and} the value of the superpi black alone conductive material The values of 136 F / g- ruthenium oxide and the conductive material of vapor-grown carbon fiber alone showed higher values than 126 F / g- ruthenium oxide.

<Effect of invention 6>

The effects of the effects 3, 4 and 5 of the present invention can produce excellent conductive effects in the ruthenium oxide supercapacitors as well as supercapacitors using metal oxides, and can be applied to supercapacitors using activated carbon materials.

1 shows a schematic diagram of a process for the production of ruthenium oxide, ruthenium oxide electrode and supercapacitor,

Figure 2 shows the thermal analysis of the ruthenium oxide prepared in Example 1 of the present invention,

Figure 3 shows the particle size distribution analysis results according to the ultrasonic dispersion of super p. Black (super p. Black) in Example 1 of the present invention,

Figure 4 is an electron scanning micrograph of the original superpi black and superpi black ultrasonically dispersed for 30 minutes in Example 1 of the present invention, Figures 4a and 4b is a photograph of the original superpi black, Figure 4c Shows a picture of superpi black, ultrasonically dispersed for 30 minutes,

Figure 5 shows an electron scanning micrograph of the vapor-grown carbon fiber in Example 1 of the present invention,

Figure 6 shows an electron scanning micrograph of the amorphous ruthenium oxide prepared by the heat treatment in Example 1 of the present invention,

7 shows particle size analysis results of amorphous ruthenium oxide prepared by heat treatment in Example 1 of the present invention and an electrode mixture using the same, and particle size distribution of superpi black and vapor-grown carbon fiber dispersed by ultrasonic wave for 30 minutes.

FIG. 8 is a scanning electron micrograph of an electrode made of an electrode material of amorphous ruthenium oxide prepared by heat treatment in Example 1 of the present invention.

9 shows a cyclic potential current curve of an electrode using an amorphous ruthenium oxide prepared by heat treatment in Example 1 of the present invention,

10 shows a cyclic potential current curve of an electrode using an amorphous ruthenium oxide prepared by heat treatment in Example 1 of the present invention,

11 shows a cyclic potential current curve of an electrode using an amorphous ruthenium oxide prepared by heat treatment in Example 1 of the present invention,

12 shows the charge / discharge curves of the first cycle in the constant current charge / discharge test of the supercapacitor using amorphous ruthenium oxide prepared by heat treatment in Example 1 of the present invention.

FIG. 13 shows the results of an AC impedance test of a supercapacitor using amorphous ruthenium oxide prepared by heat treatment in Example 1 of the present invention.

14 shows the specific capacitance obtained from the cyclic potential current curve of an electrode using ruthenium oxide prepared by heat treatment at a temperature in the range of 120 to 150 ° C. in Examples 1 to 4 according to the heat treatment temperature.

FIG. 15 shows X-ray diffraction results of ruthenium oxide prepared by heat treatment at a temperature in the range of 120 to 150 ° C. in Examples 1 to 4 of the present invention.

16 shows a change in specific capacitance of an electrode according to the concentration of sulfuric acid electrolyte in Example 5 of the present invention,

17 is a surface electron scanning micrograph of the ruthenium oxide electrode in Comparative Example 1 of the present invention,

FIG. 18 shows a cyclic potential current curve of a ruthenium oxide electrode applied with a conductive carbon fiber alone conductive material in Comparative Example 1 of the present invention.

FIG. 19 shows the charge / discharge curves of the first cycle during the constant current charge / discharge test of a supercapacitor using ruthenium oxide electrode applied with a vapor-grown carbon fiber conductive material in Comparative Example 1 of the present invention.

FIG. 20 shows the results of an AC impedance test of a supercapacitor using ruthenium oxide electrode applied with a conductive carbon fiber-only conductive material in Comparative Example 1 of the present invention.

FIG. 21 is a surface electron scanning microscope photograph of a ruthenium oxide electrode applied with a superpiblack alone conductive material in Comparative Example 2 of the present invention.

FIG. 22 illustrates a cyclic potential current curve of a ruthenium oxide electrode applied with a superpiblack alone conductive material in Comparative Example 2 of the present invention.

FIG. 23 shows the charge / discharge curves of the first cycle during the constant current charge / discharge test of the supercapacitor using the ruthenium oxide electrode applied with the superpiblack alone conductive material in Comparative Example 2 of the present invention.

FIG. 24 shows the results of an alternating current impedance test of a supercapacitor using ruthenium oxide electrode applied with superpiblack alone conductive material in Comparative Example 2 of the present invention.

Claims (11)

A ruthenium oxide is synthesized by using a solution of alkali containing sodium hydroxide from ruthenium chloride by sol-gel preparation method, the washed ruthenium oxide is washed, dried, and heat treated at a temperature of 100 ° C. to 150 ° C. Manufacturing method. A ruthenium oxide was synthesized by using a solution of alkali containing sodium hydroxide from ruthenium chloride by sol-gel preparation, washed, dried and heat-treated at 100 ° C. to 150 ° C. to form an electrode. A method of manufacturing an electrode for a supercapacitor, which is used as a material and applied to a tantalum current collector together with a conductive material and a binder. The method of claim 2, The conductive material is a supercapacitor electrode manufacturing method, characterized in that the mixture of carbon fiber and carbon black. The method of claim 2, The conductive material is a supercapacitor electrode manufacturing method, characterized in that the mixture of carbon nanotubes and carbon black. Ruthenium oxide was synthesized by sol-gel preparation using an alkaline aqueous solution containing sodium hydroxide from ruthenium chloride, and the amorphous ruthenium oxide prepared by washing and drying the synthesized ruthenium oxide, followed by heat treatment at a temperature of 100 ° C. to 150 ° C. A supercapacitor comprising an electrode formed by coating a tantalum current collector together with a conductive material and a binder using a material, a sulfuric acid electrolyte, and a porous separator. The method of claim 5, The sulfuric acid electrolyte is a metal oxide supercapacitor, characterized in that the sulfuric acid of 3.5 to 5 molar concentration. A supercapacitor comprising an electrode comprising ruthenium oxide as an electrode material and a composite conductive material in the form of particles and fibers as a conductive material. delete delete delete delete