KR101660297B1 - Active carbon synthesized from ionic liquids, manufacturing method of the same, supercapacitor using the active carbon and manufacturing method of the supercapacitor - Google Patents
Active carbon synthesized from ionic liquids, manufacturing method of the same, supercapacitor using the active carbon and manufacturing method of the supercapacitor Download PDFInfo
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/13—Energy storage using capacitors
Abstract
The present invention relates to a porous activated carbon having a specific surface area of 2,000 to 4,000 m 2 / g and containing a nitrogen functional group and having a plurality of pores for providing a passage through which electrolyte ions are introduced or discharged, A supercapacitor using the activated carbon, and a method of manufacturing the same. According to the present invention, a supercapacitor (ultra-capacitor) having a high non-storage capacity and an energy density can be manufactured by using the porous activated carbon as an electrode active material for the positive electrode and the negative electrode.
Description
The present invention relates to activated carbon, a method for producing the same, a supercapacitor using the activated carbon, and a method for producing the same. More specifically, the present invention relates to a carbonaceous material having a specific surface area of 2,000 to 4,000 m 2 / g and containing a nitrogen functional group, The present invention relates to a porous activated carbon having a plurality of pores for providing a passage through which activated carbon is discharged, and which exhibits a high non-storage capacity, a production method thereof, a supercapacitor using the activated carbon and a method for producing the same.
Generally, a supercapacitor is also referred to as an electric double layer capacitor (EDLC), a super-capacitor, or an ultra-capacitor, which is an electrode and a conductor, and an interface (Electric double layer) in which the sign is different from each other 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 a 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. Activated carbon is mainly used as the electrode active material, and the non-storage capacity based on the electrode of commercial products is known to be about 19.3 F / cc. Generally, activated carbon used as an electrode active material of a supercapacitor is activated carbon having a surface area of 1500 m2 / g or more.
However, as the applications of supercapacitors are expanded, higher non-storage capacities and energy densities are required, and development of activated carbons that exhibit higher capacitive capacities is required.
A supercapacitor using activated carbon powder as an electrode is disclosed in Japanese Patent Application Laid-Open No. 4-44407. The electrode disclosed in this publication is a solid activated carbon electrode solidified by mixing activated carbon powder with a thermosetting resin such as phenol resin.
The problem to be solved by the present invention is to provide a porous membrane having a specific surface area of 2,000 to 4,000 m 2 / g, containing nitrogen functional groups, having a plurality of pores providing a passage through which electrolyte ions are introduced or discharged, A method for producing the same, a supercapacitor using the activated carbon, and a method for manufacturing the same.
The present invention provides a porous activated carbon having a plurality of pores, which have a specific surface area in the range of 2,000 to 4,000 m 2 / g, contain nitrogen functional groups, and provide a passage through which electrolyte ions are introduced or discharged.
The non-storage capacity of the porous activated carbon is 28 to 45 F / g.
The nitrogen content of the porous activated carbon represents 0.2 to 0.8 atomic%.
The porous activated carbon has a plate-like structure.
The present invention also relates to a method for producing a carbon nanostructure, comprising the steps of carbonizing an ionic liquid containing a nitrogen component in an inert atmosphere at a temperature in the range of 500 to 1000 占 폚, activating the carbonized product by mixing with the alkali, Neutralizing with acid and washing to obtain a porous activated carbon containing nitrogen functional groups, wherein the specific surface area of the porous activated carbon is in the range of 2,000 to 4,000 m 2 / g, and the porous activated carbon has an electrolyte ion Wherein the porous activated carbon has a plurality of pores providing a passage through which the activated carbon is discharged or discharged.
The ionic liquid is selected from the group consisting of ethylmethylimidazolium chloride (EMIM Cl), ethylmethylimidazolium dicyanamide (EMIM DCA), ethylmethylimidazolium trifluoromethanesulfonate (EMIM Otf), ethylmethylimidazolium tri (EMIM TFSI), ethylmethylimidazolium acetate (EMIM Ac), ethylmethylimidazolium hydrate (EMIM OH), ethylmethylimidazolium diethylphosphate (EMIM DEP), ethylmethylimide (EMIM Lactate), butyl methyl imidazolium chloride (BMIM Cl), butyl methylimidazolium methyl carbonate solution (BMIM MeOCO 2 ), butyl methylimide (DMEM MeOCO 2 ), ethyl methylimidazolium lactate (EMIM TFSI), butyl methylimidazolium trifluoroacetate (BMIM CF 3 < RTI ID = 0.0 > CO 2 ) and dimethylimidazolium methanesulfonate (MMIM CH 3 SO 3 ).
Wherein the activating step comprises mixing the carbonized product and the alkali at a weight ratio of 1: 1 to 10, pulverizing the mixed product, and pulverizing the pulverized product at an inert atmosphere , And the alkali may be at least one substance selected from potassium hydroxide (KOH) and sodium hydroxide (NaOH).
The non-storage capacity of the porous activated carbon is 28 to 45 F / g, the nitrogen content of the porous activated carbon is 0.2 to 0.8 atomic%, and the porous activated carbon has a plate-like structure.
The present invention also relates to a porous activated carbon having a specific surface area of 2,000 to 4,000 m 2 / g and containing a nitrogen functional group and having a plurality of pores for providing a passage through which electrolyte ions are introduced or discharged, Wherein the anode, the separator and the cathode are impregnated with an electrolytic solution, and the electrolytic solution is impregnated with an electrolytic solution, wherein the cathode, the separator and the cathode are impregnated with an electrolytic solution, A supercapacitor comprising a non-aqueous liquid electrolyte is provided.
The non-storage capacity of the porous activated carbon is 28 to 45 F / g.
The nitrogen content of the porous activated carbon represents 0.2 to 0.8 atomic%.
The porous activated carbon has a plate-like structure.
Further, the present invention relates to a method for producing a porous carbon material, which comprises mixing a porous activated carbon having a specific surface area of 2,000 to 4,000 m 2 / g and containing a nitrogen functional group and having a plurality of pores for providing a passage through which electrolyte ions are introduced or discharged, Forming a composition for a supercapacitor electrode by pressing the composition for a supercapacitor electrode into an electrode form or by coating a composition for a supercapacitor electrode with a metal foil to form an electrode, Forming a supercapacitor electrode by drying the composition at a temperature of 100 ° C to 350 ° C to form a supercapacitor electrode; forming a supercapacitor electrode on the supercapacitor electrode; The positive electrode and the negative electrode are disposed between the positive electrode and the negative electrode, And separating the separator and the negative electrode from each other, and impregnating the positive electrode, the separator and the negative electrode with a non-aqueous liquid electrolyte, wherein the porous activated carbon is prepared by mixing an ionic liquid containing a nitrogen component A step of carbonizing the resultant mixture in an inert atmosphere at a temperature, an activation treatment of mixing the carbonized product with an alkali, and a step of neutralizing and treating the activated product with an acid to obtain a supercapacitor Of the present invention.
The ionic liquid is selected from the group consisting of ethylmethylimidazolium chloride (EMIM Cl), ethylmethylimidazolium dicyanamide (EMIM DCA), ethylmethylimidazolium trifluoromethanesulfonate (EMIM Otf), ethylmethylimidazolium tri (EMIM TFSI), ethylmethylimidazolium acetate (EMIM Ac), ethylmethylimidazolium hydrate (EMIM OH), ethylmethylimidazolium diethylphosphate (EMIM DEP), ethylmethylimide (EMIM Lactate), butyl methyl imidazolium chloride (BMIM Cl), butyl methylimidazolium methyl carbonate solution (BMIM MeOCO 2 ), butyl methylimide (DMEM MeOCO 2 ), ethyl methylimidazolium lactate (EMIM TFSI), butyl methylimidazolium trifluoroacetate (BMIM CF 3 < RTI ID = 0.0 > CO 2 ) and dimethylimidazolium methanesulfonate (MMIM CH 3 SO 3 ).
Wherein the activating step comprises mixing the carbonized product and the alkali at a weight ratio of 1: 1 to 10, pulverizing the mixed product, and pulverizing the pulverized product at an inert atmosphere , And the alkali may be one or more materials selected from potassium hydroxide (KOH) and sodium hydroxide (NaOH).
The non-storage capacity of the porous activated carbon is 28 to 45 F / g, the nitrogen content of the porous activated carbon is 0.2 to 0.8 atomic%, and the porous activated carbon has a plate-like structure.
The porous activated carbon of the present invention has a specific surface area in the range of 2,000 to 4,000 m 2 / g, contains a nitrogen functional group, has a plurality of pores providing a passage through which electrolyte ions are introduced or discharged, and exhibits a high non-storage capacity.
By using the porous activated carbon as an electrode active material for the positive electrode and the negative electrode, a supercapacitor having a high non-storage capacity and an energy density can be manufactured.
1 is a use state diagram of an activated carbon electrode according to the present invention.
2 is a view showing a state where a lead wire is attached to the positive electrode and the negative electrode.
3 is a view showing a state in which a book revoker is formed.
4 is a view showing a state in which the bookbinding canceller is inserted into the metal cap.
5 is a partially cut-away view of the supercapacitor.
FIG. 6 is a graph showing the specific surface area of activated carbon according to the carbonization temperature. FIG.
FIG. 7 is a graph showing a change in specific capacitance of activated carbon according to the carbonization temperature. FIG.
8 is a graph showing changes in nitrogen content in activated carbon with carbonization temperature.
9 is a field emission-scanning electron microscope (FE-SEM) photograph of activated carbon having a nitrogen functional group prepared by carbonizing at 900 ° C.
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. Wherein like reference numerals refer to like elements throughout.
The present invention relates to a porous activated carbon for a super capacitor synthesized through carbonization and activation processes using an ionic liquid, a method for producing the same, a supercapacitor using the activated carbon, and a manufacturing method thereof.
According to the present invention, it is possible to easily produce a porous activated carbon containing a nitrogen functional group by the nitrogen contained in the ionic liquid, and to control the nitrogen content, the pore structure, and the like properly by controlling the carbonization and the activation process.
The porous activated carbon according to a preferred embodiment of the present invention has a plurality of pores which have a specific surface area of 2,000 to 4,000 m 2 / g, contain nitrogen functional groups, and provide a passage through which electrolyte ions are introduced or discharged. The non-storage capacity of the porous activated carbon is 28 to 45 F / g. The nitrogen content of the porous activated carbon represents 0.2 to 0.8 atomic%. The porous activated carbon has a plate-like structure.
The method for producing porous activated carbon according to a preferred embodiment of the present invention includes the steps of carbonizing an ionic liquid containing a nitrogen component in an inert atmosphere at a temperature in the range of 500 to 1000 占 폚 and mixing the resulting carbonized product with an alkali Treating the activated product with an acid to obtain a porous activated carbon containing a nitrogen functional group, wherein the specific surface area of the porous activated carbon ranges from 2,000 to 4,000 m 2 / g , The porous activated carbon has a plurality of pores for providing a passage through which electrolyte ions are introduced or discharged. The porous activated carbon contains a nitrogen functional group by nitrogen contained in the ionic liquid.
The ionic liquid is selected from the group consisting of ethylmethylimidazolium chloride (EMIM Cl), ethylmethylimidazolium dicyanamide (EMIM DCA), ethylmethylimidazolium trifluoromethanesulfonate (EMIM Otf), ethylmethylimidazolium tri (EMIM TFSI), ethylmethylimidazolium acetate (EMIM Ac), ethylmethylimidazolium hydrate (EMIM OH), ethylmethylimidazolium diethylphosphate (EMIM DEP), ethylmethylimide (EMIM Lactate), butyl methyl imidazolium chloride (BMIM Cl), butyl methylimidazolium methyl carbonate solution (BMIM MeOCO 2 ), butyl methylimide (DMEM MeOCO 2 ), ethyl methylimidazolium lactate (EMIM TFSI), butyl methylimidazolium trifluoroacetate (BMIM CF 3 < RTI ID = 0.0 > CO 2 ) and dimethylimidazolium methanesulfonate (MMIM CH 3 SO 3 ).
Wherein the activating step comprises mixing the carbonized product and the alkali at a weight ratio of 1: 1 to 10, pulverizing the mixed product, and pulverizing the pulverized product at an inert atmosphere , And the alkali may be at least one substance selected from potassium hydroxide (KOH) and sodium hydroxide (NaOH).
The non-storage capacity of the porous activated carbon is 28 to 45 F / g, the nitrogen content of the porous activated carbon is 0.2 to 0.8 atomic%, and the porous activated carbon has a plate-like structure.
A supercapacitor according to a preferred embodiment of the present invention comprises porous activated carbon having a plurality of pores providing a passage through which the electrolyte ions enter or exit, containing nitrogen functionalities and having a specific surface area in the range of 2,000 to 4,000 m 2 / g , The porous activated carbon is used as an electrode active material for an anode and a cathode, and a separation membrane for preventing the short circuit between the anode and the cathode is disposed between the anode and the cathode, and the anode, the separation membrane, And the electrolytic solution is composed of a non-aqueous liquid electrolyte.
The non-storage capacity of the porous activated carbon is 28 to 45 F / g.
The nitrogen content of the porous activated carbon represents 0.2 to 0.8 atomic%.
The porous activated carbon has a plate-like structure.
A method of manufacturing a supercapacitor according to a preferred embodiment of the present invention is a method of manufacturing a supercapacitor having a specific surface area of 2,000 to 4,000 m 2 / g and containing a nitrogen functional group and having a plurality of pores providing a passage through which electrolyte ions are introduced or discharged The method comprising the steps of: preparing a composition for a supercapacitor electrode by mixing a conductive material, a binder and a dispersion medium; forming an electrode form by pressing the composition for the supercapacitor electrode; Forming a supercapacitor electrode by pressing the composition for a supercapacitor electrode into a sheet state and attaching it to a metal foil to form an electrode; and drying the resultant product at a temperature of 100 to 350 DEG C to form a supercapacitor electrode And the supercapacitor electrode is used as an anode and a cathode, and the amount And separating the positive electrode, the separator and the negative electrode from each other to prevent the short circuit between the positive electrode and the negative electrode between the positive electrode and the negative electrode, and impregnating the positive electrode, the separator and the negative electrode with the non-aqueous electrolyte, A step of carbonizing the ionic liquid in an inert atmosphere at a temperature in the range of 500 to 1000 占 폚, a step of activating the carbonized product by mixing with the alkali, and a step of neutralizing the activated product with an acid Cleaning step.
The ionic liquid is selected from the group consisting of ethylmethylimidazolium chloride (EMIM Cl), ethylmethylimidazolium dicyanamide (EMIM DCA), ethylmethylimidazolium trifluoromethanesulfonate (EMIM Otf), ethylmethylimidazolium tri (EMIM TFSI), ethylmethylimidazolium acetate (EMIM Ac), ethylmethylimidazolium hydrate (EMIM OH), ethylmethylimidazolium diethylphosphate (EMIM DEP), ethylmethylimide (EMIM Lactate), butyl methyl imidazolium chloride (BMIM Cl), butyl methylimidazolium methyl carbonate solution (BMIM MeOCO 2 ), butyl methylimide (DMEM MeOCO 2 ), ethyl methylimidazolium lactate (EMIM TFSI), butyl methylimidazolium trifluoroacetate (BMIM CF 3 < RTI ID = 0.0 > CO 2 ) and dimethylimidazolium methanesulfonate (MMIM CH 3 SO 3 ).
Wherein the activating step comprises mixing the carbonized product and the alkali at a weight ratio of 1: 1 to 10, pulverizing the mixed product, and pulverizing the pulverized product at an inert atmosphere , And the alkali may be one or more materials selected from potassium hydroxide (KOH) and sodium hydroxide (NaOH).
The non-storage capacity of the porous activated carbon is 28 to 45 F / g, the nitrogen content of the porous activated carbon is 0.2 to 0.8 atomic%, and the porous activated carbon has a plate-like structure.
Hereinafter, a method for producing the porous activated carbon will be described in more detail.
An ionic liquid containing a nitrogen component is prepared. The ionic liquid is selected from the group consisting of ethylmethylimidazolium chloride (EMIM Cl), ethylmethylimidazolium dicyanamide (EMIM DCA), ethylmethylimidazolium trifluoromethanesulfonate (EMIM Otf), ethylmethylimidazolium tri (EMIM TFSI), ethylmethylimidazolium acetate (EMIM Ac), ethylmethylimidazolium hydrate (EMIM OH), ethylmethylimidazolium diethylphosphate (EMIM DEP), ethylmethylimide (EMIM Lactate), butyl methyl imidazolium chloride (BMIM Cl), butyl methylimidazolium methyl carbonate solution (BMIM MeOCO 2 ), butyl methylimide (DMEM MeOCO 2 ), ethyl methylimidazolium lactate (EMIM TFSI), butyl methylimidazolium trifluoroacetate (BMIM CF 3 < RTI ID = 0.0 > CO 2 ) and dimethylimidazolium methanesulfonate (MMIM CH 3 SO 3 ).
The ionic liquid is carbonized. The carbonization is preferably performed in an inert atmosphere at a temperature of about 500 to 1000 DEG C for 10 minutes to 12 hours. The inert gas atmosphere means a gas atmosphere such as nitrogen (N 2 ), argon (Ar), and helium (He).
The pulverized product is subjected to a carbonization treatment. The milling may be performed by ball milling, jet milling or the like. As a specific example of the milling process, the ball milling process will be described. The carbonized product is charged into a ball milling machine, and is pulverized by rotating it at a constant speed using a ball milling machine. The size of the balls, the milling time, the rotation speed of the ball miller, and the like are adjusted so as to be crushed to the target particle size. As the milling time increases, the particle size gradually decreases, thereby increasing the specific surface area. The balls used for ball milling can be ceramic balls such as alumina (Al 2 O 3 ), zirconia (ZrO 2 ), and the balls may be all the same size or may be used together with balls having two or more sizes It is possible. The size of the ball, the milling time, and the rotation speed per minute of the ball mill are adjusted. For example, the size of the ball is set in a range of about 1 to 30 mm, and the rotation speed of the ball mill is about 50 to 500 rpm And ball milling can be performed for 1 to 48 hours.
Activation treatment is performed on the pulverized product. In the activation treatment, the carbonized product is mixed with an alkali such as potassium hydroxide (KOH), sodium hydroxide (NaOH) and the like at a weight ratio of 1: 1 to 10, and the mixture is pulverized. Lt; / RTI > in an inert atmosphere for a period of time.
After the activation treatment, an acid such as hydrochloric acid (HCl), nitric acid (HNO 3 ), sulfuric acid (H 2 SO 4 ) or phosphoric acid (H 3 PO 4 ) is neutralized to remove the alkali component, Clean thoroughly. After cleaning, sufficiently dry at a temperature of about 100 to 180 DEG C for 10 minutes to 6 hours.
The porous activated carbon powder having a nitrogen functional group having a specific surface area in the range of 2,000 to 4,000 m 2 / g can be obtained by the above-described process.
Hereinafter, a method of manufacturing a supercapacitor using the porous activated carbon will be described.
A method of manufacturing a supercapacitor according to a preferred embodiment of the present invention includes the steps of: preparing a composition for a supercapacitor electrode by mixing a porous activated carbon having a nitrogen functional group, a conductive material, a binder and a dispersion medium; Forming an electrode in the form of an electrode by coating the composition for the supercapacitor electrode on the metal foil or forming the electrode for the supercapacitor electrode by rolling the composition for the supercapacitor electrode into a sheet state and attaching it to the metal foil; Forming a supercapacitor electrode by drying the resultant product in an electrode form at a temperature of 100 ° C to 350 ° C; and using the supercapacitor electrode as an anode and a cathode, wherein the anode and the cathode A separator for preventing a short circuit is disposed, and the anode, the separator, And impregnating the negative electrode with the non-aqueous liquid electrolyte.
Wherein the composition for the supercapacitor electrode comprises 100 parts by weight of the porous activated carbon, 2 to 20 parts by weight of the conductive material with respect to 100 parts by weight of the porous activated carbon, 2 to 20 parts by weight of the binder with respect to 100 parts by weight of the porous activated carbon, To 200 parts by weight of the dispersion medium.
The non-aqueous liquid electrolyte may be an electrolytic solution in which at least one salt selected from TEABF4 and TEMABF4 is dissolved in at least one solvent selected from propylene carbonate, acetonitrile and sulfolane.
In addition, the non-aqueous liquid electrolyte may be composed of at least one ionic liquid selected from EMIBF4 and EMITFSI.
Hereinafter, a manufacturing method of the supercapacitor will be described in more detail with reference to Fig.
A composition for a supercapacitor electrode comprising the above-described porous activated carbon, a conductive material, a binder, and a dispersion medium is prepared. Wherein the composition for the supercapacitor electrode comprises 100 parts by weight of the porous activated carbon, 2 to 20 parts by weight of the conductive material with respect to 100 parts by weight of the porous activated carbon, 2 to 20 parts by weight of the binder with respect to 100 parts by weight of the porous activated carbon, To 200 parts by weight of the dispersion medium. The composition for the supercapacitor electrode may be difficult to uniformly mix (completely disperse) because it is a dough phase. It may be stirred for a predetermined time (for example, 10 minutes to 12 hours) using a mixer such as a planetary mixer A composition for a supercapacitor electrode suitable for electrode production can be obtained. A mixer such as a planetary mixer enables the preparation of compositions for uniformly mixed supercapacitor electrodes.
The binder may be selected from the group consisting of polytetrafluoroethylene (PTFE), polyvinylidenefluoride (PVdF), carboxymethylcellulose (CMC), polyvinyl alcohol (PVA), polyvinyl butyral vinyl butyral (PVB), poly-N-vinylpyrrolidone (PVP), styrene butadiene rubber (SBR), polyamide-imide, polyimide One or more selected ones may be used in combination.
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 dispersion medium may be an organic solvent such as ethanol (EtOH), acetone, isopropyl alcohol, N-methylpyrrolidone (NMP), propylene glycol (PG) or water.
A composition for a supercapacitor electrode may be formed by pressing a composition for a supercapacitor electrode mixed with a porous carbon, a porous activator, a binder, a conductive material, and a dispersion medium to form an electrode, or a composition for the supercapacitor electrode may be coated on a metal foil to form an electrode, Is formed into a sheet by pushing it with a roller and attached to a metal foil to form an electrode, and the resultant is dried at a temperature of 100 to 350 DEG C to form an electrode.
More specifically explaining an example of the step of forming the electrode, the composition for a supercapacitor electrode can be pressed and formed by using a roll press molding machine. The roll press forming 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 press is preferably 5 to 20 ton / cm 2, and the roll temperature is preferably 0 to 150 ° C. The composition for a supercapacitor electrode that has undergone the press-bonding process as described above is subjected to a drying process according to the present invention. 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 at least 100 캜 and not exceeding 350 캜. The drying process is preferably carried out at the above temperature for about 10 minutes to 6 hours. Such a drying process improves the strength of the supercapacitor electrode by drying the composition for the supercapacitor electrode (evaporating the dispersion medium) and binding the powder particles together.
The super capacitor electrode manufactured as described above can be applied to a small coin type super capacitor with a high capacity.
FIG. 1 is a sectional view of a coin-type supercapacitor to which the
The coin type supercapacitor includes a positive electrode made of the above-described supercapacitor electrode, a negative electrode made of the above-described supercapacitor electrode, a separator disposed between the positive electrode and the negative electrode, Is placed in a metal cap, and an electrolyte solution in which an electrolyte is dissolved is injected between the anode and the cathode, followed by sealing with a gasket.
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.
Meanwhile, the electrolytic solution filled in the supercapacitor of the present invention is a non-aqueous solution, and at least one solvent selected from among propylene carbonate (PC), acetonitrile (AN) and sulfolane (SL), tetraethylammonium tetrafluoborate ) And TEMABF4 (triethylmethylammonium tetrafluoborate) may be used. The electrolytic solution may be composed of at least one ionic liquid selected from 1-ethyl-3-methyl imidazolium tetrafluoroborate (EMIBF4) and 1-ethyl-3-methyl imidazolium bis (trifluoromethanesulfonyl) imide.
FIGS. 2 to 5 are views showing a supercapacitor according to another example of the present invention, and a method of manufacturing the supercapacitor will be described in detail with reference to FIGS. 2 to 5. FIG.
The method for preparing the composition for a supercapacitor electrode by mixing the above-mentioned porous activated carbon, the binder, the conductive material and the dispersion medium is the same as the method described above in the first embodiment.
The composition for the supercapacitor electrode may be coated on a metal foil such as an aluminum foil or an aluminum etching foil or the composition for a supercapacitor electrode may be rolled in a sheet state Rubber type) and attached to a metal foil to produce an anode and a cathode. The aluminum etched foil means that the aluminum foil is etched in a concavo-convex shape.
The anode and cathode shapes as described above are 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 at least 100 캜 and not exceeding 350 캜. The drying process is preferably carried out at the above temperature for about 10 minutes to 6 hours. Such a drying process improves the strength of the supercapacitor electrode by drying the composition for supercapacitor electrode (evaporating the dispersion medium) and binding the powder particles.
As shown in FIG. 2, the
3, the
The
As shown in Fig. 4, a sealing
The electrolytic solution is injected so that the rolled
The super capacitor manufactured in this manner is schematically shown in Fig.
Hereinafter, experimental examples according to the present invention will be specifically shown, and the present invention is not limited by the following experimental examples.
Ethylmethylimidazolium dicyanamide (EMIM DCA) containing a nitrogen component as an ionic liquid was carbonized in a nitrogen atmosphere. The carbonization treatment was carried out at 500, 600, 700, 800, 900 ° C (carbonization temperature) for 1 hour, respectively.
The carbonized product and calcium hydroxide (KOH) were mixed at a weight ratio of 1: 4 and pulverized using a dry ball milling process. The ball milling process used zirconia balls, the size of the balls was about 5 mm, the rotation speed of the ball milling machine was set to about 100 rpm, and the ball milling was performed for 2 hours.
Activation samples mixed with carbonized product and potassium hydroxide were charged into a nickel (Ni) reactor and activation treatment was carried out in an argon (Ar) atmosphere at 900 ° C for 2 hours.
The activated sample was neutralized with hydrochloric acid (HCl) and washed with distilled water to obtain a porous activated carbon, which is an electrode active material for a supercapacitor.
The thus prepared porous activated carbon is composed of porous carbon containing nitrogen functional groups by the nitrogen of the ionic liquid and having numerous pores for providing a passage through which electrolyte ions, dispersion medium, etc. are introduced or discharged.
FIG. 6 is a graph showing the specific surface area of activated carbon according to the carbonization temperature. FIG.
Referring to FIG. 6, as the carbonization temperature increases, the specific surface area of activated carbon decreases. The specific surface area of the porous activated carbon was 2800 ~ 3800 ㎡ / g and the highest specific surface area was obtained at the carbonization temperature of 500 ℃.
FIG. 7 is a graph showing a change in specific capacitance of activated carbon according to the carbonization temperature. FIG.
Referring to FIG. 7, as the carbonization temperature increases, the non-storage capacity of the activated carbon increases. The specific capacity of the porous activated carbon was 30 ~ 43 F / g, and the highest capacity was obtained at the carbonization temperature of 900 ℃.
8 is a graph showing changes in nitrogen content in activated carbon with carbonization temperature.
Referring to FIG. 8, as the carbonization temperature increases, the nitrogen content in the activated carbon increases. The nitrogen content of the porous activated carbon was 0.3 ~ 0.75 at%, and it showed the highest nitrogen content at the carbonization temperature of 900 ℃.
9 is a field emission-scanning electron microscope (FE-SEM) photograph of activated carbon having a nitrogen functional group prepared by carbonizing at 900 ° C.
Referring to FIG. 9, it can be seen that the activated carbon has a plate-like structure.
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, This is possible.
10: super capacitor electrode 50: metal cap
60: Membrane 70: Gasket
110: working electrode 120: positive electrode
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
195: Lithium foil
Claims (16)
Containing a nitrogen functional group,
A porous activated carbon having a plurality of pores providing a passage through which electrolyte ions are introduced or discharged,
The porous activated carbon has a plate-like structure,
The nitrogen content of the porous activated carbon is from 0.2 to 0.8 atomic%
Wherein the non-storage capacity of the porous activated carbon is 28 to 45 F / g.
Mixing the carbonized product with an alkali to perform an activation treatment; And
Neutralizing the activated product with an acid and washing the activated carbon to obtain a porous activated carbon containing a nitrogen functional group,
The specific surface area of the porous activated carbon ranges from 2,000 to 4,000 m 2 / g,
The porous activated carbon has a plurality of pores for providing a passage through which electrolyte ions are introduced or discharged,
The porous activated carbon has a plate-like structure,
The nitrogen content of the porous activated carbon is from 0.2 to 0.8 atomic%
Wherein the non-storage capacity of the porous activated carbon is 28 to 45 F / g.
Mixing the carbonized product with the alkali at a weight ratio of 1: 1 to 10;
Pulverizing the mixed product; And
Heat treating the pulverized product in an inert atmosphere at a temperature of 600 to 1000 DEG C,
Wherein the alkali is at least one material selected from potassium hydroxide (KOH) and sodium hydroxide (NaOH).
The porous activated carbon is used as an electrode active material for the positive electrode and the negative electrode,
A separation membrane for preventing a short circuit between the anode and the cathode is disposed between the anode and the cathode,
Wherein the anode, the separator, and the cathode are impregnated with an electrolytic solution,
The electrolytic solution is composed of a non-aqueous liquid electrolyte,
The porous activated carbon has a plate-like structure,
The nitrogen content of the porous activated carbon is from 0.2 to 0.8 atomic%
And the non-storage capacity of the porous activated carbon is 28 to 45 F / g.
The composition for the supercapacitor electrode may be formed into an electrode shape by pressing the composition for the supercapacitor electrode. Alternatively, the composition for the supercapacitor electrode may be formed in an electrode form by coating the composition for the supercapacitor electrode. Alternatively, To form an electrode;
Drying the resultant product in an electrode form at a temperature of 100 ° C to 350 ° C to form a supercapacitor electrode; And
A supercapacitor electrode is used as a positive electrode and a negative electrode, a separation membrane for preventing the short-circuit between the positive electrode and the negative electrode is disposed between the positive electrode and the negative electrode, and the positive electrode, the separation membrane and the negative electrode are impregnated with the non- ≪ / RTI >
In the porous activated carbon,
Carbonizing the ionic liquid containing the nitrogen component in an inert atmosphere at a temperature in the range of 500 to 1000 占 폚;
Mixing the carbonized product with an alkali to perform an activation treatment; And
Neutralizing the activated product with an acid and washing the activated product,
The porous activated carbon has a plate-like structure,
The nitrogen content of the porous activated carbon is from 0.2 to 0.8 atomic%
Wherein the non-storage capacity of the porous activated carbon is 28 to 45 F / g.
Mixing the carbonized product with the alkali at a weight ratio of 1: 1 to 10;
Pulverizing the mixed product; And
Heat treating the pulverized product in an inert atmosphere at a temperature of 600 to 1000 DEG C,
Wherein the alkali is at least one material selected from potassium hydroxide (KOH) and sodium hydroxide (NaOH).
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| KR20200057191A (en) * | 2018-11-16 | 2020-05-26 | 한국세라믹기술원 | Manufacturing method of heteroatom-doped spherical porous active carbon and manufacturing method of the supercapacitor usig the porous active carbon |
| KR20200125017A (en) * | 2019-04-25 | 2020-11-04 | 서울대학교산학협력단 | Method for manufacturing activated carbon, the activated carbon manufactured by the method, electrode including the activated carbon, and supercapacitor including the electrode |
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| KR101944247B1 (en) * | 2017-05-31 | 2019-01-31 | 한국세라믹기술원 | Manufacturing method of partially crystaline porous active carbon, supercapacitor using the active carbon and manufacturing method of the supercapacitor |
| KR102116279B1 (en) * | 2018-01-31 | 2020-05-28 | 한국세라믹기술원 | Manufacturing method of electrode active material for ultracapacitor, manufacturing method of ultracapacitor electrode and manufacturing method of ultracapacitor |
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| KR101610772B1 (en) * | 2012-04-20 | 2016-04-11 | 한국에너지기술연구원 | Anode active materials and manufacturing method thereof, and anode and lithium battery using the same |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20200057191A (en) * | 2018-11-16 | 2020-05-26 | 한국세라믹기술원 | Manufacturing method of heteroatom-doped spherical porous active carbon and manufacturing method of the supercapacitor usig the porous active carbon |
| KR102157515B1 (en) | 2018-11-16 | 2020-09-18 | 한국세라믹기술원 | Manufacturing method of heteroatom-doped spherical porous active carbon and manufacturing method of the supercapacitor usig the porous active carbon |
| KR20200125017A (en) * | 2019-04-25 | 2020-11-04 | 서울대학교산학협력단 | Method for manufacturing activated carbon, the activated carbon manufactured by the method, electrode including the activated carbon, and supercapacitor including the electrode |
| KR102242682B1 (en) | 2019-04-25 | 2021-04-21 | 서울대학교산학협력단 | Method for manufacturing activated carbon, the activated carbon manufactured by the method, electrode including the activated carbon, and supercapacitor including the electrode |
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