KR100305435B1 - Metal oxide electrode for supercapacitor and manufacturing method thereof - Google Patents
Metal oxide electrode for supercapacitor and manufacturing method thereof Download PDFInfo
- Publication number
- KR100305435B1 KR100305435B1 KR1019990039888A KR19990039888A KR100305435B1 KR 100305435 B1 KR100305435 B1 KR 100305435B1 KR 1019990039888 A KR1019990039888 A KR 1019990039888A KR 19990039888 A KR19990039888 A KR 19990039888A KR 100305435 B1 KR100305435 B1 KR 100305435B1
- Authority
- KR
- South Korea
- Prior art keywords
- activated carbon
- electrode
- manganese oxide
- supercapacitor
- metal oxide
- Prior art date
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 7
- 229910044991 metal oxide Inorganic materials 0.000 title claims description 27
- 150000004706 metal oxides Chemical class 0.000 title claims description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 115
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 93
- 239000007864 aqueous solution Substances 0.000 claims abstract description 28
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 19
- 239000000243 solution Substances 0.000 claims abstract description 14
- 229940071125 manganese acetate Drugs 0.000 claims abstract description 13
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims abstract description 13
- 239000008367 deionised water Substances 0.000 claims abstract description 7
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000002245 particle Substances 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000011230 binding agent Substances 0.000 claims description 7
- 239000011148 porous material Substances 0.000 claims description 7
- 239000003990 capacitor Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- -1 polytetrafluoroethylene Polymers 0.000 claims description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- 238000001914 filtration Methods 0.000 claims 1
- 229910052748 manganese Inorganic materials 0.000 claims 1
- 239000011572 manganese Substances 0.000 claims 1
- 238000010298 pulverizing process Methods 0.000 claims 1
- 238000007493 shaping process Methods 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 14
- 229910052799 carbon Inorganic materials 0.000 description 7
- 238000002484 cyclic voltammetry Methods 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 235000011164 potassium chloride Nutrition 0.000 description 2
- 239000001103 potassium chloride Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229940075397 calomel Drugs 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical class [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
- H01G11/46—Metal oxides
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
아몰퍼스상 망간산화물을 이용한 슈퍼캐패시터용 전극 및 그 제조 방법이 개시되어 있다. 활성탄소(activated carbon) 분말을 탈이온수에 분산시켜 활성탄소 수용액을 준비한다. 활성탄소가 충분히 분산된 후 상기 활성탄소 수용액에 과망간산칼륨 (KMnO4)을 첨가하여 활성탄소에 과망간산칼륨을 흡착시킨 과망간산칼륨 수용액을 준비한다. 별도로 아세트산망간(manganese acetate) 수용액을 준비한 후, 상기 과망간산칼륨 수용액에 아세트산망간 수용액을 혼합시켜 아몰퍼스상 망간산화물(a-MnO2·nH2O)을 형성한다. 이어서, 상기 아몰퍼스상 망간산화물을 적출하여 슈퍼캐패시터용 전극을 제조한다. 활성탄소와 망간산화물의 접촉면적 및 접촉강도가 향상되어 등가저항이 감소되고 고주파특성이 향상된다.Disclosed are an electrode for a supercapacitor using amorphous manganese oxide and a method of manufacturing the same. Activated carbon powder is dispersed in deionized water to prepare an activated carbon aqueous solution. After the activated carbon is sufficiently dispersed, potassium permanganate (KMnO 4 ) is added to the activated carbon aqueous solution to prepare an aqueous potassium permanganate solution in which potassium permanganate is adsorbed on the activated carbon. After separately preparing a manganese acetate solution, the manganese acetate solution is mixed with the aqueous potassium permanganate solution to form amorphous manganese oxide (a-MnO 2 · nH 2 O). Subsequently, the amorphous manganese oxide is removed to prepare an electrode for a supercapacitor. The contact area and the contact strength of activated carbon and manganese oxide are improved to reduce the equivalent resistance and improve the high frequency characteristics.
Description
본 발명은 슈퍼캐패시터용 금속산화물 전극 및 그의 제조방법에 관한 것이다. 보다 상세하게는, 아몰퍼스 망간산화물을 활물질로 한 전기 화학적 슈퍼 캐패시터의 금속산화물 전극 및 그 제조방법에 관한 것이다.The present invention relates to a metal oxide electrode for a supercapacitor and a method of manufacturing the same. More specifically, the present invention relates to a metal oxide electrode of an electrochemical supercapacitor using an amorphous manganese oxide as an active material, and a method of manufacturing the same.
전기화학 캐패시터는 재충전 가능한 축전지에 의해 전원공급을 받는 하이브리드 전기장치에서의 보조 에너지 저장장치로서 흥미 있는 것이다. 전기화학 이중층 캐패시터(EDLC)는 전극에서 전자적인 전하의 물리적인 분리와 그 표면에서 흡수된 전해질의 이온을 이용한다. 이러한 캐패시터들은 최적화된 파라다익 슈퍼캐패시터보다 낮은 단위 캐패시턴스를 갖는다. 예를 들어, 강산에서 아몰퍼스상의 수화된 루테늄산화물(hydrated ruthenium oxide), RuO2·nH2O, 우수한 주기성과 700 F/g의 캐패시턴스를 갖게된다. 그러나 이러한 구성은 적절한 것이지만, RuO2·nH2O이 너무 비싸기 때문에 상업적으로 유리하지 못하여 다른 물질에 대한 연구가 이루어져 왔다. 프로톤의 작은 크기가 최적의 화학적 흡착을 달성하는 데 최대의 기회를 제공하기 때문에 연구는 강산에서 안정된 물질로 제한되어 왔다. 방전속도가 전해질내에서 활동이온의 이동도에 의해 지배된다는 믿음하에 강산 전해질에 대한 선택이 보다 강화되어 왔다. 그러나 불행하게도 대부분의 전극 물질들은 강산하에서 불안정하였다.Electrochemical capacitors are of interest as auxiliary energy storage devices in hybrid electric devices powered by rechargeable batteries. An electrochemical double layer capacitor (EDLC) utilizes the physical separation of electronic charges at the electrodes and the ions of the electrolyte absorbed at its surface. These capacitors have lower unit capacitance than the optimized paradigm supercapacitors. For example, in strong acids it has amorphous hydrated ruthenium oxide, RuO 2 · nH 2 O, excellent periodicity and a capacitance of 700 F / g. However, this configuration is appropriate, but RuO 2 · nH 2 O is too expensive to be commercially advantageous and has been studied for other materials. Research has been limited to stable materials in strong acids because the small size of protons provides the greatest opportunity to achieve optimal chemisorption. The choice of strong acid electrolytes has been intensified in the belief that the rate of discharge is governed by the mobility of active ions in the electrolyte. Unfortunately, most electrode materials were unstable under strong acids.
한편, 아몰퍼스(amorphous) 망간산화물이 중성전해질, 예를 들어 염화칼륨(KCl) 하에서 슈퍼캐패시터용 전극물질로 뛰어난 성능을 갖는 것으로 본발명자에 의해 발표되었다. 그러나 아몰퍼스상의 망간산화물 자체는 상온에서 전도도가 매우 낮은 물질이기 때문에 등가저항이 매우 커서 고주파동작이 불가능할 뿐만 아니라 저주파동작에서도 저항에 의한 에너지 손실이 막대하다는 단점이 있다. 따라서 전도성이 좋은 도전성 카본을 아몰퍼스 망간산화물과 물리적으로 혼합하여 슈퍼캐퍼시터용 전극을 제작하였다.Amorphous manganese oxides, on the other hand, have been published by the present inventors as having excellent performance as electrode materials for supercapacitors under neutral electrolytes, such as potassium chloride (KCl). However, the amorphous manganese oxide itself is a material having a very low conductivity at room temperature, so its equivalent resistance is very large, and thus high frequency operation is impossible, and there is a disadvantage in that energy loss due to resistance is enormous in low frequency operation. Therefore, a conductive carbon having good conductivity was physically mixed with amorphous manganese oxide to prepare an electrode for a supercapacitor.
그러나, 이러한 도전성 카본과 아몰퍼스상 망간산화물을 물리적으로 혼합하여 제작한 슈퍼캐퍼시터용 전극은, 비표면적이 300 m2/g 정도로 매우 크고, 단위 질량당 캐퍼시턴스가 약 200 내지 300 F/g 인 아몰퍼스상 망간산화물을 도전성 카본과 물리적으로 혼합하기 때문에 단위부피당 포함되는 망간산화물의 양이 크지 않게 된다. 따라서 작은 부피에서 고용량을 나타내는 소자개발에 한계가 있게 된다.However, the supercapacitor electrode produced by physically mixing such conductive carbon and amorphous manganese oxide has a very large specific surface area of about 300 m 2 / g and a capacitance per unit mass of about 200 to 300 F / g. Since the amorphous manganese oxide is physically mixed with the conductive carbon, the amount of manganese oxide contained per unit volume is not large. Therefore, there is a limit to the development of a device showing a high capacity in a small volume.
다음으로, 이러한 단순한 물리적 혼합방법은 아몰퍼스상 망간산화물과 도전성 카본의 접촉면적에 있어서 한계를 가지고 있을 뿐만 아니라, 분산도라는 측면에서도 그 한계를 나타낼 수밖에 없다.Next, such a simple physical mixing method not only has a limit in the contact area between amorphous manganese oxide and conductive carbon, but also has a limit in terms of dispersion.
본 발명의 목적은, 중성전해질하에서도 슈퍼캐퍼시터용 전극물질로서 뛰어난 성능을 가지면서도 등가저항이 작고 고주파특성이 향상된 슈퍼캐퍼시터용 금속산화물 전극을 제공하는 것이다.An object of the present invention is to provide a metal oxide electrode for a supercapacitor, which has excellent performance as an electrode material for a supercapacitor even under a neutral electrolyte, and has a small equivalent resistance and improved high frequency characteristics.
도 1은 본 발명의 일 실시예에 따른 슈퍼캐패시터용 금속산화물 전극을 제작한 후 20 mV/sec의 전압주사속도로 CV(Cyclic Voltammogram)를 측정한 도면이다.1 is a view of measuring a CV (Cyclic Voltammogram) at a voltage scanning speed of 20 mV / sec after fabricating a metal oxide electrode for a supercapacitor according to an embodiment of the present invention.
도 2a 내지 도 2f는 도 1과 동일한 전극에 대하여 전압주사속도를 변화시키면서 측정한 CV 도면이다.2A to 2F are CV diagrams measured while varying the voltage scanning speed with respect to the same electrode as in FIG. 1.
도 3은 본 발명의 일 실시예에 따른 슈퍼캐패시터용 금속산화물 전극에 대하여 전압주사속도를 달리하면서 측정한 단위 캐패시턴스의 변화를 나타낸 도면이다.3 is a view showing a change in unit capacitance measured while varying the voltage scanning speed with respect to the metal oxide electrode for the supercapacitor according to an embodiment of the present invention.
도 4는 본 발명의 일 실시예에 따른 슈퍼캐패시터용 금속산화물 전극에 대하여 활성탄소의 표면적을 달리하면서 측정한 단위캐패시턴스의 변화를 나타낸 도면이다.4 is a view showing a change in unit capacitance measured while varying the surface area of activated carbon with respect to the metal oxide electrode for the supercapacitor according to an embodiment of the present invention.
도 5는 본 발명의 일 실시예에 따른 슈퍼캐패시터용 금속산화물 전극에 대한 X선 회절분석 결과도면이다.5 is an X-ray diffraction analysis result of the metal oxide electrode for the supercapacitor according to an embodiment of the present invention.
도 6은 본 발명의 일 실시예에 따른 슈퍼캐패시터용 금속산화물 전극에 대한 활성탄소의 함량비에 따른 단위캐패시턴스의 변화를 도시한 도면이다.6 is a view showing a change in unit capacitance according to the content ratio of activated carbon to the metal oxide electrode for the supercapacitor according to an embodiment of the present invention.
상기 본 발명의 목적을 달성하기 위하여, 본 발명은 특정의 형상으로 제작된슈퍼캐패시터용 금속산화물 전극에 있어서, 상기 전극은, 활성탄소의 내부기공 및 외부표면상에 코팅된 망간산화물의 분말입자와 이들을 결합시켜주는 바인더의 혼합물로 이루어진 슈퍼캐패시터용 금속산화물 전극을 제공한다.In order to achieve the object of the present invention, the present invention is a metal oxide electrode for a supercapacitor manufactured in a specific shape, the electrode is powder particles of manganese oxide coated on the inner pores and outer surface of the activated carbon and these Provided is a metal oxide electrode for a supercapacitor comprising a mixture of binders to bond.
본 발명은 또한, 활성탄소(activated carbon) 분말을 탈이온수에 분산시켜 활성탄소 수용액을 준비하는 단계, 상기 활성탄소 수용액에 과망간산칼륨(KMnO4)을 첨가하여 활성탄소에 과망간산칼륨을 흡착시킨 과망간산칼륨 수용액을 준비하는 단계, 아세트산망간(manganese acetate) 수용액을 준비하는 단계, 상기 과망간산칼륨 수용액에 상기 아세트산망간 수용액을 혼합시켜 아몰퍼스상 망간산화물(a-MnO2·nH2O)을 형성하는 단계, 및 상기 아몰퍼스상 망간산화물을 적출하여 슈퍼캐패시터용 전극을 제작하는 단계로 이루어진 슈퍼캐패시터용 금속산화물 전극의 제작 방법을 제공한다.The invention also, of activated carbon (activated carbon) of potassium permanganate was followed by dispersion of the powder in deionized water absorption of potassium permanganate in phase, activated carbon was added to potassium permanganate (KMnO 4) the activated carbon aqueous solution to prepare the activated carbon aqueous solution Preparing an aqueous solution, preparing an aqueous solution of manganese acetate, mixing the aqueous solution of manganese acetate with the aqueous potassium permanganate solution to form an amorphous manganese oxide (a-MnO 2 · nH 2 O), and The present invention provides a method of manufacturing a supercapacitor metal oxide electrode, comprising extracting the amorphous manganese oxide to produce a supercapacitor electrode.
본 발명에 의하면, 수용액상에서 아몰퍼스상 망간산화물을 화학반응법에 의해 합성하는 과정에서 표면적이 큰 활성탄소를 미리 참여시켜, 활성탄소의 내부기공 및 외부표면에 아몰퍼스상 망간산화물이 형성되도록 한다.According to the present invention, in the process of synthesizing the amorphous manganese oxide in an aqueous solution by the chemical reaction method, the active carbon having a large surface area participates in advance so that the amorphous manganese oxide is formed in the inner pores and the outer surface of the activated carbon.
본 발명의 일 실시예에 따른 슈퍼캐퍼시터용 금속산화물 전극의 제조 방법은, 먼저, 활성탄소(activated carbon) 분말을 탈이온수에 분산시켜 활성탄소 수용액을 준비한다. 활성탄소가 충분히 분산된 후 상기 활성탄소 수용액에 과망간산칼륨 (KMnO4)을 첨가하여 활성탄소에 과망간산칼륨을 흡착시킨 과망간산칼륨 수용액을 준비한다. 별도로 아세트산망간(manganese acetate) 수용액을 준비한 후, 상기 과망간산칼륨 수용액에 아세트산망간 수용액을 혼합시켜 아몰퍼스상 망간산화물(a-MnO2·nH2O)을 형성한다. 이어서, 상기 아몰퍼스상 망간산화물을 적출하여 슈퍼캐패시터용 전극을 제작한다.In the method of manufacturing a metal oxide electrode for a supercapacitor according to an embodiment of the present invention, first, an activated carbon powder is dispersed in deionized water to prepare an activated carbon aqueous solution. After the activated carbon is sufficiently dispersed, potassium permanganate (KMnO 4 ) is added to the activated carbon aqueous solution to prepare an aqueous potassium permanganate solution in which potassium permanganate is adsorbed on the activated carbon. After separately preparing a manganese acetate solution, the manganese acetate solution is mixed with the aqueous potassium permanganate solution to form amorphous manganese oxide (a-MnO 2 · nH 2 O). Subsequently, the amorphous manganese oxide is removed to prepare an electrode for a supercapacitor.
상기 아몰퍼스상 망간산화물로부터 전극을 제작하는 단계는, 상기 아몰퍼스상 망간산화물의 분말입자를 상기 혼합된 수용액으로부터 필터링, 워싱 및 건조시켜 적출한 후, 상기 아몰퍼스상 망간산화물의 분말입자를 분쇄하고, 상기 아몰퍼스상 망간산화물의 분쇄물에 바인더를 혼합한 후, 상기 혼합물을 특정 형상으로 형상화하여 전극을 형성한다.In the preparing of the electrode from the amorphous manganese oxide, the powder particles of the amorphous manganese oxide are filtered, washed and dried from the mixed aqueous solution, and then the powder particles of the amorphous manganese oxide are pulverized, and After the binder is mixed with the pulverized amorphous manganese oxide, the mixture is shaped into a specific shape to form an electrode.
상기 활성탄소의 함량은 상기 아몰퍼스 망간산화물 분말의 총량에 대하여 20 내지 80 중량%가 되도록 분산시키며, 그 표면적이 1500 내지 3000 m2/g 인 것을 사용하며, 보다 바람직하게는 상기 활성탄소의 함량은 40 중량%이며, 그 표면적이 2000 m2/g 인 것을 사용한다.The content of the activated carbon is dispersed to 20 to 80% by weight based on the total amount of the amorphous manganese oxide powder, the surface area is used is 1500 to 3000 m 2 / g, more preferably the content of the activated carbon is 40 weight % And its surface area is 2000 m 2 / g.
한편, 본 발명의 다른 실시예에 따른 슈퍼캐패시터용 금속산화물 전극은, 특정의 형상으로 제작된 슈퍼캐패시터용 금속산화물 전극에 있어서, 활성탄소의 내부기공 및 외부표면상에 코팅된 망간산화물의 분말입자와 이들을 결합시켜주는 바인더의 혼합물로 이루어진다.On the other hand, the supercapacitor metal oxide electrode according to another embodiment of the present invention, in the supercapacitor metal oxide electrode manufactured in a specific shape, and the powder particles of manganese oxide coated on the inner pores and outer surface of the activated carbon It consists of a mixture of binders that bind them together.
상기 활성탄소의 함량은 상기 망간산화물 분말입자의 총량에 대하여 20 내지 80 중량%가 되며, 상기 활성탄소는 그 표면적이 1500 내지 3000 m2/g 인 것을 사용한다. 또한, 상기 망간산화물은 활성탄소가 미리 분산된 수용액에 과망간산칼륨을 0.01 몰(mole) 첨가하여 활성탄소의 내부기공 및 외부표면에 흡착시킨 수용액과, 아세트산망간이 0.015 몰(mole) 첨가된 수용액을 반응시켜 형성된 것이다.The content of the activated carbon is 20 to 80% by weight based on the total amount of the manganese oxide powder particles, the activated carbon is used that the surface area of 1500 to 3000 m 2 / g. In addition, the manganese oxide reacts the aqueous solution in which potassium permanganate is added to the aqueous solution in which the activated carbon is dispersed in advance and adsorbed to the inner pores and the outer surface of the activated carbon, and the aqueous solution in which the manganese acetate is added to 0.015 mol (mole) is reacted. It is formed by.
이하, 본 발명의 바람직한 실시예를 첨부한 도면을 참조하여 상세히 설명한다.Hereinafter, with reference to the accompanying drawings, preferred embodiments of the present invention will be described in detail.
먼저, 본 발명에 따른 슈퍼캐퍼시터용 금속산화물 전극의 형성과정을 구체적으로 살펴본다.First, the formation process of the metal oxide electrode for the supercapacitor according to the present invention will be described in detail.
1) 60 ml의 탈이온수에 일정량의 활성탄소 분말을 첨가한 후 완전히 습윤(wetting)되어 수용액내에 분산되도록 저어준다. 활성탄소의 종류는 BP-15, BP-20, BP-25, MSC-30의 4가지를 사용하였다. 이들 활성탄소는 표면적이 서로 다른 것으로써, 각기 뒤의 숫자에 100배한 것이 표면적이다. 예를 들어, BP-20은 20×100, 즉 2000 m2/g의 표면적을 갖는 활성탄소를 나타낸다.1) After adding a certain amount of activated carbon powder to 60 ml of deionized water, completely wet and stir to disperse in aqueous solution. Four types of activated carbon were used, BP-15, BP-20, BP-25, and MSC-30. These activated carbons have different surface areas, which are 100 times the number after each. For example, BP-20 represents activated carbon with a surface area of 20 × 100, ie 2000 m 2 / g.
활성탄소의 함량은 각기 20 중량%, 40 중량%, 60 중량%, 80 중량%가 되도록 첨가하였다. 여기서 중량%는 과망간산칼륨과 아세트산망간을 후속되는 조성으로 혼합하여 합성된 망간산화물 분말의 총량을 기준으로 하여 첨가된 활성탄소의 중량비를 의미한다.The activated carbon was added in amounts of 20 wt%, 40 wt%, 60 wt%, and 80 wt%, respectively. Here, the weight% means a weight ratio of activated carbon added based on the total amount of manganese oxide powder synthesized by mixing potassium permanganate and manganese acetate in a subsequent composition.
2) 이후, 1.58g의 과산화망간(KMnO4)을 첨가하여 1시간 이상 저어주면서 활성탄소에 과산화망간의 흡착이 충분히 일어날 수 있도록 한다. 초기의 활성탄소가 분산된 과산화망간의 수용액은 원래의 과산화망간 수용액의 색인 짙은 보라색을 띄게 되지만 충분한 시간 이후에는 활성탄소의 강력한 흡착능에 의해 수용액내의 과산화망간이 모두 활성탄소의 내부기공 표면 및 외부표면에 흡착되기 때문에 투명하게 변한다.2) After that, add 1.58 g of manganese peroxide (KMnO 4 ) to stir for more than 1 hour to allow sufficient adsorption of manganese peroxide to activated carbon. Initially, the aqueous solution of manganese peroxide in which activated carbon is dispersed becomes dark purple of the original solution of manganese peroxide, but after sufficient time, all of the manganese peroxide in the aqueous solution is adsorbed on the inner pore surface and the outer surface of the activated carbon due to the strong adsorption capacity of the activated carbon. It becomes transparent.
3) 별도로 100 ml의 탈이온수에 3.68 g의 아세트산망간(Manganese acetate)을 첨가하여 수용액을 제조한다.3) Separately, 3.68 g of manganese acetate is added to 100 ml of deionized water to prepare an aqueous solution.
4) 이어서, 상기 활성탄소가 첨가된 과산화망간 수용액에 상기 아세트산망간 수용액을 혼합하여 격렬하게 저어준다. 두 수용액을 혼합하면 아몰퍼스 망간산화물의 형성반응은 매우 빨리 일어난다. 따라서 혼합직후 혼합용액의 색이 아몰퍼스상 망간산화물의 색인 갈색으로 바로 변하며, 혼합용액의 점도도 급격히 증가하게 된다. 혼합용액을 12시간 이상 스터링하여 반응이 충분히 일어나도록 한다.4) Then, the manganese acetate solution is mixed with the manganese peroxide solution to which the activated carbon is added and stirred vigorously. When the two aqueous solutions are mixed, the formation reaction of amorphous manganese oxide occurs very quickly. Therefore, immediately after mixing, the color of the mixed solution immediately changes to the brown color of amorphous manganese oxide, and the viscosity of the mixed solution also increases rapidly. Stir the mixed solution for at least 12 hours to allow sufficient reaction.
5) 이어서, 짙은 갈색의 아몰퍼스 망간산화물의 분산입자를 세라믹 필터로 수차례 필터링하고 탈이온수로 워싱한 후 120℃ 정도로 유지되는 건조기에서 충분히 건조시킨다. 여기서 생성물의 아몰퍼스 특성을 확인하기 위하여 X선 회절분석을 실시한다.5) Subsequently, the dark brown amorphous manganese oxide dispersed particles were filtered several times with a ceramic filter, washed with deionized water, and dried sufficiently in a drier maintained at about 120 ° C. X-ray diffraction analysis is performed here to confirm amorphous properties of the product.
도 5는 본 발명의 전술한 BP-20의 활성탄소를 40 중량% 첨가하여 제조한 망간산화물에 대한 X선 회절분석 결과도면이다. 도면으로부터 결정성이 다소 있으나 미는 통상의 이산화망간과 비교하면 결정화도가 매우 미미하여 아몰퍼스상이라 할 수 있다.5 is an X-ray diffraction analysis of the manganese oxide prepared by adding 40% by weight of the activated carbon of the above-described BP-20 of the present invention. Although the crystallinity is somewhat from the figure, the taste is very amorphous compared to the conventional manganese dioxide crystals can be called amorphous phase.
6) 이어서, 충분히 건조된 아몰퍼스 망간산화물 분산입자를 분쇄한 후, 바인더(binder)로서 5 중량%의폴리테트라플루오로에틸렌(polytetrafluoroethylene;PTFE)와 혼합한다. 이어서, 혼합물을 롤링하여 일정한 두께를 갖는 시트형상으로 만든다. 이어서 시트형상의 전극을 절단하여 펠릿형상으로 만든 후 집전체(current collector)상에냉간압연시켜 슈퍼캐패시터용 전극을 제작한다.6) Then, the sufficiently dried amorphous manganese oxide dispersed particles are pulverized and mixed with 5% by weight of polytetrafluoroethylene (PTFE) as a binder. The mixture is then rolled into a sheet with a constant thickness. Subsequently, the sheet electrode is cut into pellets, and then cold rolled onto a current collector to fabricate a supercapacitor electrode.
도 1은 활성탄소 BP-20이 40 중량% 포함된 아몰퍼스상 망간산화물을 활물질로 하여 전극을 제작한 후 20 mV/sec의 전압주사속도로 CV(Cyclic Voltammogram)를 측정한 도면이다.FIG. 1 is a view of measuring a CV (Cyclic Voltammogram) at a voltage scanning speed of 20 mV / sec after fabricating an electrode using an amorphous manganese oxide containing 40 wt% of activated carbon BP-20 as an active material.
전극의 성능평가는 활동전극(working electrode), 백금-가제(platinum-gauze) 카운터전극 및 SCE(standard calomel reference electrode)가 장착된 비이커형 전기화학 셀에서 수행된다. 활동전극의 표면적은 0.25 cm2, 전해질은 pH 6.7로 조정된 2M KCl 수용액이다.Performance evaluation of the electrodes is performed in a beaker type electrochemical cell equipped with a working electrode, a platinum-gauze counter electrode and a standard calomel reference electrode (SCE). The surface area of the active electrode is 0.25 cm 2 , and the electrolyte is a 2M KCl aqueous solution adjusted to pH 6.7.
도 1로부터 본 발명에 따른 전극의 캐패시터는 전사이클에 대하여 일정한 비율로 충전 및 방전이 이루어짐을 알 수 있으며, 전류반응성이 매우 빠름을 알 수 있다.It can be seen from FIG. 1 that the capacitor of the electrode according to the present invention is charged and discharged at a constant rate for the entire cycle, and that the current reactivity is very fast.
도 2a 내지 도 2f는 도 1과 동일한 조성을 갖는 전극에 대하여 전압주사속도를 변화시키면서 측정한 CV 도면이다. 주사속도가 20 mV/sec 일 때 이상적인 캐패시터의 성능을 나타냄을 알 수 있다.2A to 2F are CV diagrams measured while varying the voltage scanning speed with respect to the electrode having the same composition as in FIG. 1. It can be seen that the performance of the ideal capacitor is shown when the scanning speed is 20 mV / sec.
도 3은 본 발명의 슈퍼캐패시터용 금속산화물 전극에 대하여 전압주사속도를 달리하면서 측정한 단위캐패시턴스(specific capacitance)의 변화를 나타낸 도면이다. 여기서 단위캐패시턴스는 활성탄소에 코팅된 이산화망간의 무게에 대해 측정된 캐패시턴스값을 나누어서 표준화한 값을 의미한다.3 is a view showing a change in specific capacitance measured while varying the voltage scanning speed with respect to the metal oxide electrode for supercapacitor of the present invention. Here, unit capacitance means a standardized value obtained by dividing the measured capacitance value with respect to the weight of manganese dioxide coated on activated carbon.
도 3으로부터, 주사속도가 빨라질수록 단위캐패시턴스가 감소함을 알 수 있으며, 전압주사속도가 10 mV/sec 및 20 mV/sec 인 경우 단위캐패시턴스가 300 F/g 이상임을 알 수 있다.3, it can be seen that the unit capacitance decreases as the scanning speed increases, and when the voltage scanning speeds are 10 mV / sec and 20 mV / sec, the unit capacitance is 300 F / g or more.
도 4는 본 발명의 일 실시예에 따른 슈퍼캐패시터용 금속산화물 전극에 대하여 활성탄소의 표면적을 달리하면서 측정한 단위캐패시턴스의 변화를 나타낸 도면으로써, 표면적이 다른 활성탄소를 40 중량%로 동일한 양을 이용하여 형성된 아몰퍼스 이산화망간을 활물질로 하여 제조한 전극의 단위캐패시턴스를 비교한 것이다.4 is a view showing the change in unit capacitance measured while varying the surface area of the activated carbon for the metal oxide electrode for the supercapacitor according to an embodiment of the present invention, using the same amount of the active carbon having a different surface area by 40% by weight The unit capacitance of the electrode manufactured by using amorphous manganese dioxide as an active material is compared.
도면으로부터, BP-20(표면적 2000 m2/g)을 사용한 경우에 가장 큰 단위캐패시턴스값을 얻을 수 있다는 것을 알 수 있다.From the figure, it can be seen that the largest unit capacitance value can be obtained when BP-20 (surface area 2000 m 2 / g) is used.
도 6은 각기 다른 표면적을 갖는 활성탄소를 이용하여 활성탄소에 코팅된 이산화망간으로부터 본 발명의 슈퍼캐패시터용 금속산화물 전극을 만들고, 이들에 대한 활성탄소의 함량비에 따른 단위캐패시턴스의 변화를 측정하여 도시한 도면이다.6 shows a metal oxide electrode for a supercapacitor of the present invention from manganese dioxide coated on activated carbon by using activated carbon having different surface areas, and measures changes in unit capacitance according to the content ratio of activated carbon thereto. Drawing.
도 6으로부터, 표면적이 2000 m2/g인 활성탄소를 40 중량%가 되도록 첨가한 경우에 가장 큰 단위캐패시턴스값을 나타냄을 알 수 있다.It can be seen from FIG. 6 that the largest unit capacitance value is shown when activated carbon having a surface area of 2000 m 2 / g is added to 40 wt%.
본 발명에 따르면, 슈퍼캐패시터용 전극물질로써, 망간산화물만을 사용하거나 도전성 카본을 단순히 혼합한 경우에 비하여 단위면적당 망간산화물의 로딩량이크게 증대될 뿐만 아니라, 분산도의 측면에서도 크게 향상됨을 알 수 있다. 따라서 본 발명에 따른 전극은 활성탄소와 망간산화물의 접촉면적의 증대 및 접촉강도의 향상으로 등가저항이 크게 감소하고, 높은 단위캐패시턴스를 갖기 때문에 고주파특성이 향상된다는 효과가 있다.According to the present invention, as the electrode material for the supercapacitor, the loading amount of manganese oxide per unit area is increased not only significantly but also in terms of dispersion degree as compared with the case of using only manganese oxide or simply mixing conductive carbon. . Therefore, the electrode according to the present invention has an effect that the equivalent resistance is greatly reduced by increasing the contact area of the activated carbon and the manganese oxide and improving the contact strength, and the high frequency characteristic is improved because of the high unit capacitance.
이상의 본 발명의 실시예는 본 발명의 권리범위를 제한하는 것은 아니며, 본 발명의 사상의 범위내에서 다양한 변경 및 변화가 있음을 당업자에게 있어서는 당연한 것이다.The above embodiments of the present invention do not limit the scope of the present invention, and it is natural for those skilled in the art that various changes and modifications can be made within the scope of the present invention.
Claims (8)
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019990039888A KR100305435B1 (en) | 1999-09-16 | 1999-09-16 | Metal oxide electrode for supercapacitor and manufacturing method thereof |
| US09/514,366 US6339528B1 (en) | 1999-09-16 | 2000-02-28 | Metal oxide electrode for supercapacitor and manufacturing method thereof |
| JP2000080308A JP3978302B2 (en) | 1999-09-16 | 2000-03-22 | Metal oxide electrode for supercapacitor and method for producing the same |
| US09/971,652 US6616875B2 (en) | 1999-09-16 | 2001-10-09 | Manufacturing method for a metal oxide electrode for supercapacitor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019990039888A KR100305435B1 (en) | 1999-09-16 | 1999-09-16 | Metal oxide electrode for supercapacitor and manufacturing method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR20010025128A KR20010025128A (en) | 2001-04-06 |
| KR100305435B1 true KR100305435B1 (en) | 2001-11-07 |
Family
ID=19611883
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1019990039888A KR100305435B1 (en) | 1999-09-16 | 1999-09-16 | Metal oxide electrode for supercapacitor and manufacturing method thereof |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR100305435B1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100508234B1 (en) * | 2002-11-29 | 2005-08-17 | 주식회사 기노리텍 | Manufacturing method of metaloxide for super capacitor and manufacturing methode of metaloxidic super capacitor |
| KR100622737B1 (en) * | 2004-11-08 | 2006-09-19 | 현대자동차주식회사 | Preparing method of manganese oxide-carbon nanocomposite powder for supercapacitor electrode manufacture |
| KR101045563B1 (en) * | 2009-12-01 | 2011-07-01 | 한국과학기술연구원 | Electrode comprising a metal oxide coated carbon particles, an electrochemical capacitor having the same and a method of manufacturing the same |
-
1999
- 1999-09-16 KR KR1019990039888A patent/KR100305435B1/en active IP Right Grant
Also Published As
| Publication number | Publication date |
|---|---|
| KR20010025128A (en) | 2001-04-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3978302B2 (en) | Metal oxide electrode for supercapacitor and method for producing the same | |
| US5797971A (en) | Method of making composite electrode materials for high energy and high power density energy storage devices | |
| Zhang et al. | Nanowire Na0. 35MnO2 from a hydrothermal method as a cathode material for aqueous asymmetric supercapacitors | |
| Lee et al. | Supercapacitor behavior with KCl electrolyte | |
| EP1876663B1 (en) | Negative electrode active material for charging device | |
| Malak et al. | Hybrid materials for supercapacitor application | |
| US8451584B2 (en) | Solid state energy storage device and method | |
| US6097588A (en) | Electrode materials from hydrous metal and/or hydrous mixed metal oxides | |
| JP5468416B2 (en) | Lithium-air secondary battery and method for producing air electrode thereof | |
| US9159502B2 (en) | Supercapacitor with hexacyanometallate cathode, activated carbon anode, and non-aqueous electrolyte | |
| Zhang et al. | Mild synthesis route to nanostructured α-MnO2 as electrode materials for electrochemical energy storage | |
| Patrick et al. | A novel synthesis strategy for hybrid quaternary rGO/MnO2/NiO/CuO nanocomposite as electrode for enduring symmetric supercapacitor fabrication | |
| Song et al. | Freestanding CuV2O6/carbon nanotube composite films for flexible aqueous zinc-ion batteries | |
| Yan et al. | Energizing hybrid supercapacitors by using Mn 2+-based active electrolyte | |
| Gupta et al. | SrFeO 3− δ: a novel Fe 4+↔ Fe 2+ redox mediated pseudocapacitive electrode in aqueous electrolyte | |
| Mohamed et al. | An electrode for a high-performance asymmetric supercapacitor made of rGO/PANI/PB ternary nanocomposite | |
| KR100305435B1 (en) | Metal oxide electrode for supercapacitor and manufacturing method thereof | |
| Gromadskyi et al. | Cyclic voltammetric study of tin hexacyanoferrate for aqueous battery applications | |
| CN108493006B (en) | Preparation method of manganese silicate/carbohydrate button type supercapacitor | |
| Li et al. | Asymmetric supercapacitors with dominant pseudocapacitance based on manganese oxide nanoflowers in a neutral aqueous electrolyte | |
| CN115995351A (en) | Preparation method of transition metal nickel doped manganese dioxide electrode material | |
| CN112420401B (en) | Bismuth oxide/manganese oxide composite supercapacitor and preparation method thereof | |
| CN113658809B (en) | Preparation method of amorphous manganese oxide electrode material | |
| Yesmin et al. | Exploration of Cu/gC 3 N 4 Nanocomposites as a Cost-Effective High-Performance Asymmetric Supercapacitor Electrode Material | |
| KR100305436B1 (en) | Methal oxide electrode for supercapacitor and menufacturing method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A201 | Request for examination | ||
| N231 | Notification of change of applicant | ||
| A302 | Request for accelerated examination | ||
| G15R | Request for early publication | ||
| N231 | Notification of change of applicant | ||
| E701 | Decision to grant or registration of patent right | ||
| GRNT | Written decision to grant | ||
| FPAY | Annual fee payment |
Payment date: 20130528 Year of fee payment: 13 |
|
| FPAY | Annual fee payment |
Payment date: 20140617 Year of fee payment: 14 |
|
| FPAY | Annual fee payment |
Payment date: 20150616 Year of fee payment: 15 |
|
| FPAY | Annual fee payment |
Payment date: 20160712 Year of fee payment: 16 |
|
| FPAY | Annual fee payment |
Payment date: 20170627 Year of fee payment: 17 |
|
| FPAY | Annual fee payment |
Payment date: 20180628 Year of fee payment: 18 |