KR101936044B1 - Supercapacitor electrode for high temperature, manufactureing method of the electrode, and Supercapacitor for high temperature using the electrode - Google Patents

Supercapacitor electrode for high temperature, manufactureing method of the electrode, and Supercapacitor for high temperature using the electrode Download PDF

Info

Publication number
KR101936044B1
KR101936044B1 KR1020170029894A KR20170029894A KR101936044B1 KR 101936044 B1 KR101936044 B1 KR 101936044B1 KR 1020170029894 A KR1020170029894 A KR 1020170029894A KR 20170029894 A KR20170029894 A KR 20170029894A KR 101936044 B1 KR101936044 B1 KR 101936044B1
Authority
KR
South Korea
Prior art keywords
electrode
active material
electrode active
temperature
supercapacitor
Prior art date
Application number
KR1020170029894A
Other languages
Korean (ko)
Other versions
KR20180103251A (en
Inventor
노광철
김주연
한조아
Original Assignee
한국세라믹기술원
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 한국세라믹기술원 filed Critical 한국세라믹기술원
Priority to KR1020170029894A priority Critical patent/KR101936044B1/en
Publication of KR20180103251A publication Critical patent/KR20180103251A/en
Application granted granted Critical
Publication of KR101936044B1 publication Critical patent/KR101936044B1/en

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/52—Separators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/78—Cases; Housings; Encapsulations; Mountings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

Abstract

The present invention relates to an electrode active material, 0.1 to 20 parts by weight of a conductive material with respect to 100 parts by weight of the electrode active material, and 1 to 20 parts by weight of a binder with respect to 100 parts by weight of the electrode active material, To 5 atomic%, a method for producing the electrode, and a high-temperature super capacitor using the electrode for the high-temperature super-capacitor. According to the present invention, it is possible to prevent deterioration of electrochemical performance by minimizing the oxygen functional groups present in the electrode active material, to reduce gas generation of the electrolyte when used as an electrode active material of a high-temperature supercapacitor, The cost can be high and the decomposition voltage can be increased.

Figure 112017023460197-pat00007

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrode for a high-temperature super capacitor, a method of manufacturing the same, and a high-temperature supercapacitor employing the electrode for the high-temperature supercapacitor.

The present invention relates to an electrode for a high-temperature super capacitor, a method of manufacturing the electrode, and a high-temperature supercapacitor, and more particularly, to a method for manufacturing an electrode for a high-temperature supercapacitor, which can prevent deterioration of electrochemical performance by minimizing oxygen functional groups present in the electrode active material, The present invention relates to a supercapacitor electrode capable of reducing the generation of gas of an electrolyte and having a high storage cost and a high decomposition voltage at a high temperature of the supercapacitor, a method of manufacturing the same, and a supercapacitor using the supercapacitor electrode.

Generally, a supercapacitor is also referred to as an electric double layer capacitor (EDLC) or an ultracapacitor, which is formed by a pair of electrodes and a conductor, each having a different sign at the interface of the electrolyte solution immersed in the electrode and the conductor, (Electric double layer) of the charge / discharge operation is used, and the deterioration due to the repetition of the charging / discharging operation is very small, so that the device is not required to be repaired. As a result, supercapacitors are widely used in IC (integrated circuit) backup of various electric and electronic devices. Recently, they have been widely used for toys, solar energy storage, HEV (hybrid electric vehicle) have.

Such a supercapacitor generally includes two electrodes of a positive electrode and a negative electrode impregnated with an electrolytic solution, a separator of a porous material interposed between the two electrodes to enable ion conduction only and to prevent insulation and short circuit, A gasket for preventing leakage of electricity and preventing insulation and short-circuit, and a metal cap as a conductor for packaging them. Then, one or more unit cells (normally 2 to 6 in the case of the coin type) are stacked in series and the two terminals of the positive and negative electrodes are combined.

The performance of the supercapacitor is determined by the electrode active material and the electrolyte. In particular, the main performance such as the capacitance is largely determined by the electrode active material. As such an electrode active material, activated carbon is mainly used.

However, the activated carbon prepared by a method such as an alkali activation and a steam activation method has a certain amount of oxygen functional groups on its surface, which causes a side reaction with the electrolyte during charging and discharging, resulting in a decrease in electrochemical performance. Side reactions during the electrochemical reaction with the oxygen functional groups remaining on the activated carbon may show a decrease in the electrochemical performance.

In particular, in the case of a high-temperature supercapacitor for use at a high temperature, since the amount of gas generated by the reaction between the oxygen functional group remaining in the activated carbon and the electrolytic solution increases, a measure is required to prevent the deterioration of electrochemical performance have.

Korean Patent Publication No. 10-1079317

A problem to be solved by the present invention is to minimize deterioration of electrochemical performance by minimizing oxygen functional groups present in an electrode active material and to reduce gas generation of an electrolyte when used as an electrode active material of a high temperature super capacitor, A supercapacitor electrode having a high storage cost and a high decomposition voltage at a high temperature, a method of manufacturing the same, and a supercapacitor using the supercapacitor electrode.

The present invention relates to an electrode active material, 0.1 to 20 parts by weight of a conductive material with respect to 100 parts by weight of the electrode active material, and 1 to 20 parts by weight of a binder with respect to 100 parts by weight of the electrode active material, To 5 atomic%.

The electrode active material may include one or more carbon materials selected from carbon nanotubes, graphene, and activated carbon.

According to another aspect of the present invention, there is provided a method of manufacturing an electrode active material, comprising the steps of: preparing an electrode active material; heat treating the electrode active material to reduce the content of oxygen functional groups contained in the electrode active material; A step of forming a composition for a high-temperature super capacitor electrode by mixing a binder, a binder and a dispersion medium; and a step of forming a composition for the high-temperature supercapacitor electrode by pressing the composition for the high- Forming a high-temperature supercapacitor electrode composition in an electrode form by pressing the high-temperature supercapacitor electrode composition with a roller to form a sheet state and attaching the composition to a metal foil or a current collector to form an electrode; Forming an electrode for a high-temperature supercapacitor, ≪ / RTI >

The heat treatment is preferably performed at a temperature of 500 to 1100 캜.

The heat treatment is preferably performed in a reducing or inert gas atmosphere.

The electrode active material may include one or more carbon materials selected from carbon nanotubes, graphene, and activated carbon.

It is preferable that the content of the oxygen functional group of the electrode active material reduced in the oxygen functional group by the heat treatment is 1.5 to 5 atomic%.

It is preferable that 0.1 to 20 parts by weight of the conductive material and 100 to 20 parts by weight of the binder are mixed with 100 parts by weight of the electrode active material to form the composition for the high temperature super capacitor electrode.

The present invention also provides a method of manufacturing a high-temperature supercapacitor, which comprises: a step of forming a thin film of a high-temperature supercapacitor, which comprises a positive electrode made of the electrode for the high-temperature supercapacitor, a negative electrode made of the electrode for the high-temperature supercapacitor, a separator disposed between the positive electrode and the negative electrode, And a gasket for sealing the metal cap, wherein the anode, the separator, and the cathode are disposed inside and are filled with an electrolyte solution.

The present invention also provides a method of manufacturing a thin film transistor comprising a first separator for preventing a short circuit, a positive electrode comprising the electrode for the high-temperature supercapacitor, a second separator for preventing the short-circuit between the positive electrode and the negative electrode, A first lead connected to the negative electrode, a second lead connected to the positive electrode, a metal cap accommodating the negative revolver, and a second lead connected to the negative cap, And a sealing rubber for sealing, wherein the roll revolver is impregnated with an electrolytic solution.

According to the present invention, the deterioration of the electrochemical performance can be prevented by minimizing the oxygen functional groups present in the electrode active material. By minimizing the content of oxygen functional groups contained in the electrode active material by the heat treatment, gas generation of the electrolyte can be reduced when used as an electrode active material of the high-temperature supercapacitor, and the storage cost can be increased at a high temperature of the supercapacitor .

1 is a cross-sectional view of a coin type supercapacitor according to an example.
2 to 5 are views showing a winding type super capacitor according to an example.
FIG. 6 is a graph showing X-ray photoelectron spectroscopy (XPS) analysis results of activated carbon (electrode active material) reduced in oxygen functional group by heat treatment according to Example 1 and commercial activated carbon used in Comparative Example.
7 is a graph showing electrochemical characteristics of a high-temperature super capacitor cell manufactured according to Example 1 and Comparative Example.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, it should be understood that the following embodiments are provided so that those skilled in the art will be able to fully understand the present invention, and that various modifications may be made without departing from the scope of the present invention. It is not.

Hereinafter, the term 'high-temperature super-capacitor' refers to a supercapacitor for use at 85 to 140 ° C.

Activated carbon produced by methods such as alkali activation and steam activation has a certain amount of oxygen functional groups on its surface. Side reaction during the electrochemical reaction by the oxygen functional groups remaining on the activated carbon may show a deterioration of the electrochemical performance and lead to a decrease in the electrochemical performance accompanied with a side reaction with the electrolyte during charge and discharge.

In the present invention, it is possible to prevent the deterioration of electrochemical performance by minimizing the oxygen functional groups present in the electrode active material, to reduce the generation of gas of the electrolyte when used as an electrode active material of a high-temperature super capacitor, A supercapacitor electrode having a high decomposition voltage, a method of manufacturing the same, and a supercapacitor using the supercapacitor electrode.

The electrode for a high-temperature supercapacitor according to a preferred embodiment of the present invention comprises an electrode active material, 0.1 to 20 parts by weight of a conductive material with respect to 100 parts by weight of the electrode active material, and 1 to 20 parts by weight of a binder with respect to 100 parts by weight of the electrode active material , And the electrode active material has an oxygen functional group content of 1.5 to 5 atomic%.

The electrode active material may include one or more carbon materials selected from carbon nanotubes, graphene, and activated carbon.

A method of manufacturing an electrode for a high-temperature supercapacitor according to a preferred embodiment of the present invention includes the steps of preparing an electrode active material, heat treating the electrode active material to reduce the content of oxygen functional groups contained in the electrode active material, Mixing the electrode active material, the conductive material, the binder and the dispersion medium, in which the oxygen functional group has been reduced by a high-temperature super capacitor electrode composition, to form a composition for a high-temperature super capacitor electrode; Forming an electrode shape by coating a composition for a supercapacitor electrode on a metal foil or a current collector; or pushing the composition for a high-temperature supercapacitor electrode into a sheet state and attaching the composition to a metal foil or a current collector, The resultant product was dried to obtain a high-temperature supercapacitor electrode And a step of sex.

The heat treatment is preferably performed at a temperature of 500 to 1100 캜.

The heat treatment is preferably performed in a reducing or inert gas atmosphere.

The electrode active material may include one or more carbon materials selected from carbon nanotubes, graphene, and activated carbon.

It is preferable that the content of the oxygen functional group of the electrode active material reduced in the oxygen functional group by the heat treatment is 1.5 to 5 atomic%.

It is preferable that 0.1 to 20 parts by weight of the conductive material and 100 to 20 parts by weight of the binder are mixed with 100 parts by weight of the electrode active material to form the composition for the high temperature super capacitor electrode.

A high-temperature super capacitor according to a preferred embodiment of the present invention includes a positive electrode made of the electrode for the high-temperature supercapacitor, a negative electrode made of the electrode for the high-temperature supercapacitor, and a negative electrode disposed between the positive electrode and the negative electrode, A separator for preventing a short circuit, a metal cap having the anode, the separator, and the cathode disposed therein and having an electrolyte injected therein, and a gasket for sealing the metal cap.

According to another aspect of the present invention, there is provided a high-temperature supercapacitor including: a first separator for preventing a short circuit; a positive electrode formed of the electrode for the high-temperature supercapacitor; a second separator for preventing short- A first lead wire connected to the negative electrode, a second lead wire connected to the positive electrode, and a second lead wire connected to the negative electrode, wherein the negative lead made of the electrode for high temperature super capacitor is stacked and coiled in a roll form, A metal cap, and a sealing rubber for sealing the metal cap, wherein the roll canceller is impregnated with an electrolytic solution.

Hereinafter, the method of manufacturing the high-temperature super capacitor electrode and the super capacitor using the super capacitor electrode will be described more specifically.

Generally, the supercapacitor is used at room temperature, and the high-temperature super capacitor is a supercapacitor for use at a temperature higher than room temperature, 85 to 140 ° C.

An electrode active material is prepared to manufacture such a high-temperature super capacitor. The electrode active material may include one or more carbon materials selected from carbon nanotubes, graphene, and activated carbon. The electrode active material preferably has a specific surface area in the range of 1,000 to 3,300 m 2 / g. The electrode active material has a certain amount of oxygen functional groups, which are present in the form of CO, COC, OC = O, chemisorbed oxygen, etc. in the electrode active material.

The electrode active material is heat-treated in a reduced or inert gas atmosphere to reduce the content of oxygen functional groups contained in the electrode active material. The inert gas atmosphere is a gas atmosphere containing an inert gas such as argon (Ar) gas, helium (He) gas or nitrogen (N 2 ) gas. The reducing gas atmosphere is a gas atmosphere containing a gas such as hydrogen (H 2 ). The heat treatment is preferably performed at a temperature of 500 to 1100 캜. The heat treatment is preferably performed in a reactor made of a material such as stainless steel which can withstand the heat treatment temperature and does not react with the electrode active material at the time of heat treatment. For example, in general, commercial activated carbon contains about 5 to 10 atomic% of oxygen functional groups. By performing the heat treatment, the content of oxygen functional groups contained in activated carbon can be reduced to about 1.5 to 5 atomic%. By minimizing the content of oxygen functional groups contained in the electrode active material by the heat treatment, gas generation of the electrolyte can be reduced when used as an electrode active material of the high-temperature supercapacitor, and the storage cost can be increased at a high temperature of the supercapacitor .

A composition for a high temperature super capacitor electrode is prepared by mixing the electrode active material, the conductive material, the binder and the dispersion medium having reduced oxygen functional groups by the heat treatment.

The composition for a high-temperature super capacitor electrode comprises 0.1 to 20 parts by weight of a conductive material with respect to 100 parts by weight of the electrode active material and the electrode active material, 1 to 20 parts by weight of a binder with respect to 100 parts by weight of the electrode active material, 100 to 300 parts by weight of the dispersion medium.

The conductive material is not particularly limited as long as it is an electron conductive material which does not cause a chemical change. Examples of the conductive material include natural graphite, artificial graphite, carbon black, acetylene black, Ketjen black, Super-P black, carbon fiber, , Metal powder such as aluminum and silver, or metal fiber. The conductive material is preferably contained in the composition for the high-temperature super capacitor electrode in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of the electrode active material.

The binder may be selected from the group consisting of polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), carboxymethylcellulose (CMC), polyvinyl alcohol (PVA), polyvinyl butyral polyvinyl butyral (PVB), poly-N-vinylpyrrolidone (PVP), styrene butadiene rubber (SBR), polyamide-imide, polyimide Can be used alone or in combination of two or more. The binder is preferably contained in the composition for the high-temperature super capacitor electrode in an amount of 1 to 20 parts by weight based on 100 parts by weight of the electrode active material.

The solvent may be an organic solvent such as ethanol (EtOH), acetone, isopropyl alcohol, N-methyl pyrrolidone (NMP), propylene glycol (PG) or water. The dispersion medium is preferably contained in the composition for the high-temperature supercapacitor electrode in an amount of 100 to 300 parts by weight based on 100 parts by weight of the electrode active material.

The composition for the high-temperature super capacitor electrode may be difficult to uniformly mix (completely disperse) because it is a dough-like composition. It is preferable to use a high-speed mixer such as a planetary mixer for a predetermined time Hour), a composition for a high-temperature super capacitor electrode suitable for electrode production can be obtained. A high-speed mixer, such as a planetary mixer, enables the preparation of compositions for uniformly mixed high temperature super capacitor electrodes.

A composition for a high temperature super capacitor electrode in which the electrode active material, a conductive material, a binder and a dispersion medium are mixed is formed into an electrode shape, or the composition for a high temperature super capacitor electrode is coated on a metal foil or a current collector to form an electrode, The composition for a high-temperature super capacitor electrode is formed into a sheet by pushing it with a roller and attached to a metal foil or a current collector to form an electrode. The resulting electrode is dried at a temperature of 100 ° C to 350 ° C to form an electrode do.

More specifically explaining an example of forming the electrode, the composition for the high temperature super capacitor electrode can be pressed and formed by using a roll press molding machine. The roll press molding machine aims at improving the electrode density through rolling and controlling the thickness of the electrode. The roll press forming machine is provided with a controller capable of controlling the thickness and heating temperature of rolls and rolls at the upper and lower ends, ≪ / RTI > As the electrode in the roll state passes the roll press, the rolling process is carried out and the roll is rolled again to complete the electrode. At this time, the pressing pressure of the roll press is preferably 1 to 20 ton / cm 2, and the roll temperature is preferably 0 to 150 캜. The composition for the high-temperature super capacitor electrode after the above press-bonding process is subjected to a drying process. The drying process is carried out at a temperature of 100 ° C to 350 ° C, preferably 150 ° C to 300 ° C. If the drying temperature is less than 100 ° C, evaporation of the dispersion medium is difficult and it is not preferable because oxidation of the conductive material may occur during drying at a high temperature exceeding 350 ° C. Therefore, the drying temperature is preferably 100 占 폚 or more and not exceeding 350 占 폚. The drying process is preferably carried out at the above temperature for about 10 minutes to 12 hours. Such a drying process binds the electrode active material and the conductive material particles to improve the strength of the electrode.

In another example of forming the electrode, the composition for the high-temperature supercapacitor electrode may be a metal foil such as a Ti foil, an Al foil, or an Al etching foil Alternatively, the composition for a high-temperature super capacitor electrode may be coated on a current collector, or may be formed into a sheet state (rubber type) by pressing it with a roller and attached to a metal foil or a current collector to form a positive electrode or a negative electrode. The aluminum etched foil means that the aluminum foil is etched in a concavo-convex shape. The anode or cathode shape after the above-mentioned process is subjected to a drying process. The drying process is carried out at a temperature of 100 ° C to 350 ° C, preferably 150 ° C to 300 ° C. If the drying temperature is less than 100 ° C, evaporation of the dispersion medium is difficult and it is not preferable because oxidation of the conductive material may occur during drying at a high temperature exceeding 350 ° C. Therefore, the drying temperature is preferably 100 占 폚 or more and not exceeding 350 占 폚. The drying process is preferably carried out at the above temperature for about 10 minutes to 6 hours. Through the drying process, the electrode active material and the conductive material particles are bound to improve the strength of the electrode.

The prepared electrode for a high-temperature supercapacitor includes an electrode active material, 0.1 to 20 parts by weight of a conductive material with respect to 100 parts by weight of the electrode active material, and 1 to 20 parts by weight of a binder with respect to 100 parts by weight of the electrode active material, It is preferable that the content of the oxygen functional group is 1.5 to 5 atomic%. It is possible to prevent the deterioration of electrochemical performance by minimizing the oxygen functional groups present in the electrode active material and to reduce the gas generation of the electrolyte when used as an electrode active material of the high temperature super capacitor, Can be increased.

The electrode for a high-temperature supercapacitor manufactured as described above can be applied to a small coin-type supercapacitor as shown in Fig. 1, a wound supercapacitor as shown in Figs. 2 to 5, and the like.

1 is a sectional view of a coin-type supercapacitor to which an electrode for a high-temperature supercapacitor is applied, according to an embodiment of the present invention. 1, reference numeral 190 denotes a metal cap as a conductor, 160 denotes a porous separator for insulation between the anode 120 and the cathode 110 and prevents short-circuiting, and reference numeral 192 denotes an electrolyte leakage And to prevent insulation and short circuit. At this time, the anode 120 and the cathode 110 are firmly fixed by the metal cap 190 and an adhesive.

The coin type supercapacitor includes an anode 120 made up of the electrode for a high temperature super capacitor described above, a cathode 110 made up of the electrode for the high temperature super capacitor described above, and a cathode 110 disposed between the anode 120 and the cathode 110 A separator 160 for preventing a short circuit between the anode 120 and the cathode 120 is disposed in the metal cap 190 and an electrolyte solution in which the electrolyte is dissolved between the anode 120 and the cathode 110 Injected, and then sealed with a gasket 192. [0064]

The separator may be a battery such as a polyethylene nonwoven fabric, a polypropylene nonwoven fabric, a polyester nonwoven fabric, a polyacrylonitrile porous separator, a poly (vinylidene fluoride) hexafluoropropane copolymer porous separator, a cellulose porous separator, a kraft paper or a rayon fiber, And is not particularly limited as long as it is a membrane commonly used in the field.

On the other hand, the electrolyte to be charged to a high temperature super-capacitor is propylene carbonate (PC; propylene carbonate), acetonitrile (AN; acetonitrile) and sulfolane (SL; sulfolane) in at least one solvent selected from TEABF 4 (tetraethylammonium tetrafluoborate) and TEMABF 4 (triethylmethylammonium tetrafluoborate) may be used. Also, the electrolytic solution may include one or more ionic liquids selected from 1-ethyl-3-methyl imidazolium tetrafluoroborate (EMIBF 4 ) and 1-ethyl-3-methyl imidazolium bis (trifluoromethanesulfonyl) imide .

FIGS. 2 to 5 are views showing the state of use of electrodes for high-temperature super-capacitors according to another example, and showing wound-type super-capacitors to which electrodes for high-temperature super-capacitors are applied. A method of manufacturing a wound-type supercapacitor will be described in detail with reference to Figs. 2 to 5. Fig.

As shown in FIG. 2, the lead wires 130 and 140 are attached to the positive electrode 120 and the negative electrode 110, respectively, which are made of the above-described high temperature super capacitor electrode.

3, the first separator 150, the anode 120, the second separator 160, and the working electrode (cathode 110) are laminated and coiled to form a roll And then wound around the roll with the adhesive tape 170 or the like so that the roll shape can be maintained.

The second separator 160 between the anode 120 and the cathode 110 prevents shorting between the anode 120 and the cathode 110. The first and second separation membranes 150 and 160 may be formed of any one of a polyethylene nonwoven fabric, a polypropylene nonwoven fabric, a polyester nonwoven fabric, a polyacrylonitrile porous separator, a poly (vinylidene fluoride) hexafluoropropane copolymer porous separator, a cellulose porous separator, Or a separator commonly used in the field of batteries and capacitors such as rayon fibers.

As shown in Fig. 4, a sealing rubber 180 is mounted on a roll-shaped product and is mounted on a metal cap 190 (e.g., an aluminum case).

The electrolytic solution is injected so that the roll-shaped winding element 175 (the anode 120 and the cathode 110) is impregnated and sealed. The electrolytic solution is prepared by dissolving 1 or more selected from among TEABF 4 (tetraethylammonium tetrafluoborate) and TEMABF 4 (triethylmethylammonium tetrafluoborate) in at least one solvent selected from the group consisting of propylene carbonate (PC), acetonitrile (AN) and sulfolane Or a salt in which more than two kinds of salts are dissolved can be used. Also, the electrolytic solution may include one or more ionic liquids selected from 1-ethyl-3-methyl imidazolium tetrafluoroborate (EMIBF 4 ) and 1-ethyl-3-methyl imidazolium bis (trifluoromethanesulfonyl) imide .

Fig. 5 schematically shows a winding-type supercapacitor fabricated in this manner.

According to the present invention, the deterioration of the electrochemical performance can be prevented by minimizing the oxygen functional groups present in the electrode active material. By minimizing the content of oxygen functional groups contained in the electrode active material by the heat treatment, gas generation of the electrolyte can be reduced when used as an electrode active material of the high-temperature supercapacitor, and the storage cost can be increased at a high temperature of the supercapacitor .

EXAMPLES Hereinafter, examples according to the present invention will be specifically shown, and the present invention is not limited to the following examples.

≪ Example 1 >

An electrode for high temperature super capacitor was fabricated by using commercial activated carbon as an electrode active material.

Heat treatment was performed to minimize the oxygen functional group content of the electrode active material. 50 g of YP50F as commercial activated carbon was placed in a stainless steel reactor and heat treatment was performed at 1000 캜 for 1 hour in an argon (Ar) gas atmosphere. After the heat treatment, the furnace was cooled to room temperature while maintaining the argon gas atmosphere.

An electrode for a high temperature super capacitor was prepared by using the electrode active material having reduced oxygen functional groups by the heat treatment. 0.9 g of the above electrode active material with reduced oxygen functional groups, 0.05 g of carbon black Super-P as a conductive material and 0.05 g of polytetrafluoroethylene (PTFE) as a binder were added to ethanol as a dispersion medium, And mixed with a planetary mixer for 3 minutes to prepare a composition for a high temperature super capacitor electrode in a slurry state.

The composition for the high-temperature supercapacitor electrode was processed 5 to 10 times by hand, and rolled by a roll press to produce an electrode. At this time, the pressing pressure of the press was set to 1 to 20 ton / cm 2, and the roll temperature was set to 60 ° C. At this time, the thickness of the rolled product was 200 mu m.

The rolled product was placed in a vacuum dryer at 150 ° C and dried for 12 hours to obtain an electrode for a high-temperature super capacitor.

The vacuum dried electrode was assembled into a high temperature super capacitor cell. Glass fiber was used as the separation membrane and EMIBF 4 , which is an electrolytic solution for a high temperature super capacitor, was used as an electrolyte.

<Comparative Example>

Commercial activated carbon was used as an electrode active material and used as an electrode for a high - temperature supercapacitor.

0.05 g of carbon black Super-P as a conductive material and 0.05 g of polytetrafluoroethylene (PTFE) as a binder were added to ethanol as a dispersion medium and mixed with a planetary mixer ) For 3 minutes to prepare a composition for a high-temperature super capacitor electrode in a slurry state.

The composition for the high-temperature supercapacitor electrode was processed 5 to 10 times by hand, and rolled by a roll press to produce an electrode. At this time, the pressing pressure of the press was set to 1 to 20 ton / cm 2, and the roll temperature was set to 60 ° C. At this time, the thickness of the rolled product was 200 mu m.

The rolled product was placed in a vacuum dryer at 150 ° C and dried for 12 hours to obtain an electrode for a high-temperature super capacitor.

The vacuum dried electrode was assembled into a high temperature super capacitor cell. Glass fiber was used as the separation membrane and EMIBF 4 , which is an electrolytic solution for a high temperature super capacitor, was used as an electrolyte.

Table 1 and FIG. 6 show X-ray photoelectron spectroscopy (XPS) analysis results of activated carbon (electrode active material) reduced in oxygen functional group and commercial activated carbon used in Comparative Example by heat treatment according to Example 1. In Table 1 below, the units are atomic weight percent.

division Comparative Example (Commercial Activated Carbon) Example 1 (activated carbon reduced in oxygen functional group by heat treatment) C1s 92.8 97.2 O1s 7.2 2.8

Referring to Table 1 and FIG. 6, it was confirmed that the content of oxygen functional groups of the activated carbon (electrode active material) reduced in oxygen functional group by the heat treatment according to Example 1 was lower than that of the non-heat-treated commercial activated carbon used in the comparative example.

Current capacity of the high-temperature super capacitor cell manufactured according to Example 1 and the comparative example, a rate characteristic according to the scanning speed, a leakage current, and a voltage drop (IR-drop) Cyclic voltammetry method (CV) was used. The device used for the measurement was a Potentiostat (VSP, EC-Lab, France) and was operated at a high temperature (140 ° C) with a voltage range of 0 to 2.7 V at a scanning rate of 10 mV / s. .

Referring to FIG. 7, electrochemical characteristics of a high-temperature super capacitor cell fabricated according to Example 1 were evaluated by a cyclic voltammetric method. As a result, at a high temperature (140 ° C), a scanning speed of 10 mV / s It was found that the discharge capacity satisfies 16 F / cc.

As a result of the test, when the electrode active material having the minimum oxygen functional group by heat treatment was used (Example 1), the storage cost was high and the decomposition voltage was high in the high temperature test as compared with the case where the general commercial activated carbon was used (Comparative Example).

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, but, on the contrary, This is possible.

110: cathode 120: anode
130: first lead wire 140: second lead wire
150: first separator 160: second separator
170: Adhesive tape 175: Winding element
180: sealing rubber 190: metal cap
192: Gasket

Claims (10)

0.1 to 20 parts by weight of a conductive material with respect to 100 parts by weight of the electrode active material and 1 to 20 parts by weight of a binder with respect to 100 parts by weight of the electrode active material,
The electrode active material has an oxygen functional group content of 1.5 to 5 atomic%
Wherein the electrode active material comprises at least one carbon material selected from the group consisting of carbon nanotubes and graphene.
delete Preparing an electrode active material;
Heating the electrode active material to reduce the content of oxygen functional groups contained in the electrode active material;
Preparing a composition for a high-temperature super capacitor electrode by mixing the electrode active material, the conductive material, the binder and the dispersion medium having reduced oxygen functional groups by the heat treatment;
The composition for the high-temperature super capacitor electrode may be formed into an electrode shape by pressing the composition for the high-temperature super capacitor electrode, or may be formed into an electrode shape by coating the composition for the high temperature super capacitor electrode on the metal foil or the current collector, And forming the electrode in the form of an electrode attached to a metal foil or a current collector; And
And drying the resultant formed in an electrode form to form an electrode for a high-temperature supercapacitor,
The electrode active material having reduced oxygen functional groups by the heat treatment has a content of oxygen functional groups of 1.5 to 5 atomic%
Wherein the electrode active material comprises at least one carbon material selected from the group consisting of carbon nanotubes and graphene.
The method according to claim 3, wherein the heat treatment is performed at a temperature of 500 to 1100 캜.
The method of claim 3, wherein the heat treatment is performed in a reducing atmosphere or an inert gas atmosphere.
delete delete 4. The method according to claim 3, wherein 0.1 to 20 parts by weight of a conductive material is mixed with 100 parts by weight of the electrode active material and 1 to 20 parts by weight of a binder with respect to 100 parts by weight of the electrode active material is mixed with the dispersion medium to prepare the composition for a high temperature super capacitor electrode Wherein the first electrode and the second electrode are electrically connected to each other.
A positive electrode comprising the electrode for a high-temperature supercapacitor according to claim 1;
A negative electrode comprising the electrode for a high-temperature supercapacitor according to claim 1;
A separation membrane disposed between the anode and the cathode and for preventing a short circuit between the anode and the cathode;
A metal cap in which the anode, the separator, and the cathode are disposed and into which an electrolyte is injected; And
And a gasket for sealing the metal cap.
A first separator for preventing a short circuit, a positive electrode made of the electrode for a high-temperature supercapacitor according to claim 1, a second separator for preventing short-circuiting between the positive electrode and the negative electrode, and a high-temperature supercapacitor electrode A winding element having a roll shape in which cathodes are sequentially stacked and coiled;
A first lead wire connected to the negative electrode;
A second lead wire connected to the positive electrode;
A metal cap for receiving the book revolver; And
And a sealing rubber for sealing the metal cap,
Wherein the roll revolver is impregnated in an electrolytic solution.
KR1020170029894A 2017-03-09 2017-03-09 Supercapacitor electrode for high temperature, manufactureing method of the electrode, and Supercapacitor for high temperature using the electrode KR101936044B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
KR1020170029894A KR101936044B1 (en) 2017-03-09 2017-03-09 Supercapacitor electrode for high temperature, manufactureing method of the electrode, and Supercapacitor for high temperature using the electrode

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
KR1020170029894A KR101936044B1 (en) 2017-03-09 2017-03-09 Supercapacitor electrode for high temperature, manufactureing method of the electrode, and Supercapacitor for high temperature using the electrode

Publications (2)

Publication Number Publication Date
KR20180103251A KR20180103251A (en) 2018-09-19
KR101936044B1 true KR101936044B1 (en) 2019-01-08

Family

ID=63719120

Family Applications (1)

Application Number Title Priority Date Filing Date
KR1020170029894A KR101936044B1 (en) 2017-03-09 2017-03-09 Supercapacitor electrode for high temperature, manufactureing method of the electrode, and Supercapacitor for high temperature using the electrode

Country Status (1)

Country Link
KR (1) KR101936044B1 (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102172610B1 (en) * 2019-12-06 2020-11-02 한국세라믹기술원 Manufacturing method of electrode active material for supercapacitor, manufacturing method of supercapacitor electrode for high power and supercapacitor for high power

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101137719B1 (en) * 2010-12-07 2012-04-24 한국세라믹기술원 Manufacturing method of active carbon electrode for supercapacitor
US20130183592A1 (en) 2012-01-18 2013-07-18 Samsung Electronics Co., Ltd. Porous carbonaceous composite material, positive electrode and lithium air battery including the material, and method of preparing the material
KR101635763B1 (en) 2015-08-12 2016-07-04 한국세라믹기술원 Composite for ultracapacitor electrode, manufacturing method of ultracapacitor electrode using the composite, and ultracapacitor manufactured by the method

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101137719B1 (en) * 2010-12-07 2012-04-24 한국세라믹기술원 Manufacturing method of active carbon electrode for supercapacitor
US20130183592A1 (en) 2012-01-18 2013-07-18 Samsung Electronics Co., Ltd. Porous carbonaceous composite material, positive electrode and lithium air battery including the material, and method of preparing the material
KR101635763B1 (en) 2015-08-12 2016-07-04 한국세라믹기술원 Composite for ultracapacitor electrode, manufacturing method of ultracapacitor electrode using the composite, and ultracapacitor manufactured by the method

Also Published As

Publication number Publication date
KR20180103251A (en) 2018-09-19

Similar Documents

Publication Publication Date Title
US8520367B2 (en) Method of manufacturing lithium ion capacitor and lithium ion capacitor manufactured using the same
KR101793040B1 (en) Manufacturing method of electrode active material for ultracapacitor, manufacturing method of ultracapacitor electrode using the electrode active material and ultracapacitorusing the electrode active material
CN112951612A (en) Aqueous sodium-ion battery capacitor hybrid device with bismuth oxide cathode and preparation method thereof
KR101635763B1 (en) Composite for ultracapacitor electrode, manufacturing method of ultracapacitor electrode using the composite, and ultracapacitor manufactured by the method
KR101660297B1 (en) Active carbon synthesized from ionic liquids, manufacturing method of the same, supercapacitor using the active carbon and manufacturing method of the supercapacitor
KR101166696B1 (en) Supercapacitor and manufacturing method of the same
KR102081616B1 (en) Supercapacitor having excellent stability for high voltage and method for manufacturing the same
KR101098240B1 (en) Manufacturing method of supercapacitor cell
KR101936044B1 (en) Supercapacitor electrode for high temperature, manufactureing method of the electrode, and Supercapacitor for high temperature using the electrode
KR101860755B1 (en) Composite for ultracapacitor electrode, manufacturing method of ultracapacitor electrode using the composite, and ultracapacitor manufactured by the method
KR101494615B1 (en) Manufacturing method of active carbon for supercapacitor electrode
KR102188237B1 (en) Composite for supercapacitor electrode, manufacturing method of supercapacitor electrode using the composite, and supercapacitor manufactured by the method
KR102379507B1 (en) High-density hybrid supercapacitor with phosphorine-based negative electrode and method of manufacturing thereof
KR102495330B1 (en) Manufacturing method of electrode active material for supercapacitor co-doped with nitrogen and fluorine and high power supercapacitor using the same and method of manufacturing thereof
KR102188242B1 (en) Composite for supercapacitor electrode, manufacturing method of supercapacitor electrode using the composite, and supercapacitor manufactured by the method
KR102013179B1 (en) Manufacturing method of electrode active material for supercapacitor, manufacturing method of supercapacitor electrode and manufacturing method of supercapacitor
KR101571679B1 (en) Carbon nanofiber-ionic liquids composite, manufacturing method of the same, ultra-capacitor using the composite and manufacturing method of the ultra-capacitor
KR101494622B1 (en) Composite for supercapacitor electrode and manufacturing method of supercapacitor electrode using the composite
KR102172610B1 (en) Manufacturing method of electrode active material for supercapacitor, manufacturing method of supercapacitor electrode for high power and supercapacitor for high power
KR102639923B1 (en) Manufacturing method of nitrogen doped electrode active material with reduced chemical amount by using surface modifier, and supercapacitor using the same and method of manufacturing thereof
KR102401629B1 (en) Manufacturing method of porous active carbon, manufacturing method of supercapacitor electrode using the porous active carbon and supercapacitor using the supercapacitor electrode
KR102343771B1 (en) Electrolyte of supercapacitor, high voltage supercapacitor using the same and method of manufacturing thereof
KR102561404B1 (en) Electric double layer capacitor eleclyte, electric double layer capacitor using the electrolyte and manufacturing method of the electric double layer capacitor
KR102347581B1 (en) Electrolyte of supercapacitor, high voltage supercapacitor and manufacturing method of the high voltage supercapacitor using the electrolyte
KR101409178B1 (en) Composite for supercapacitor electrode and manufacturing method of supercapacitor electrode using the composite

Legal Events

Date Code Title Description
A201 Request for examination
E902 Notification of reason for refusal
E701 Decision to grant or registration of patent right
GRNT Written decision to grant