KR102625219B1 - High-voltage and high-reliability ultra-high-capacity electric double layer capacitor and method for manufacturing thereof - Google Patents
High-voltage and high-reliability ultra-high-capacity electric double layer capacitor and method for manufacturing thereof Download PDFInfo
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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
- H01G11/54—Electrolytes
- H01G11/58—Liquid electrolytes
-
- 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
- H01G11/84—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
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
본 발명의 일 실시예에 따르는 고전압 및 고신뢰성 초고용량 전기이중층 커패시터는 양극, 음극, 분리막 및 전해액을 포함하는 전기이중층 커패시터에 있어서, 상기 양극 및 음극은 집전체 및 상기 집전체 상에 형성된 전극 활물질층을 포함하되, 상기 전극 활물질층은, 활성탄, 도전재, 및 불소가 치환된 아크릴계 바인더 및 올레핀계 바인더로부터 선택되는 1종 이상의 바인더를 포함하고, 상기 전해액은, 염(salt)으로서 스파이로-(1,1')-바이피롤리디움 테트라플루오로보레이트(spiro-(1,1')-bipyrrolidium tetrafluoroborate, SBPBF4)을 포함하고, 용매로서 아세토니트릴(Acetonitrile, AN) 및 트리스(2,2,2-트리플루오로에틸) 포스파이트(Tris(2,2,2-trifluoroethyl)phosphite, TTFP)의 혼합 용매를 포함하는 것을 특징으로 할 수 있다.The high-voltage and high-reliability ultra-high capacity electric double layer capacitor according to an embodiment of the present invention is an electric double layer capacitor including an anode, a cathode, a separator, and an electrolyte, wherein the anode and the cathode are a current collector and an electrode active material formed on the current collector. layer, wherein the electrode active material layer includes activated carbon, a conductive material, and at least one binder selected from a fluorine-substituted acrylic binder and an olefin-based binder, and the electrolyte solution is a salt containing a spiro- Contains (1,1')-bipyrrolidium tetrafluoroborate (SBPBF 4 ), and acetonitrile (AN) and tris (2,2) as solvents. , 2-trifluoroethyl) phosphite (Tris(2,2,2-trifluoroethyl)phosphite, TTFP).
Description
본 발명은 고전압 및 고신뢰성 초고용량 전기이중층 커패시터 및 이의 제조 방법에 관한 것이다.The present invention relates to a high-voltage and high-reliability ultra-high capacity electric double layer capacitor and a method of manufacturing the same.
전기화학적 원리를 이용하여 전기에너지를 저장 및 변환하는 전기화학 커패시터(Electrochemical Capacitor)는 울트라 커패시터(Ultracapacitor) 또는 초고용량 커패시터(Supercapacitor)라 불리우고 있다. 상술한 전기화학적 캐패시터는 구동 원리에 따라 크게 활성탄소를 주요 전극으로 사용하는 전기 이중충 커패시터(Electric Double Layer Capacitor, EDLC), 금속산화물 및 전도성 고분자를 전극으로 사용하는 유사커패시터(Pseudo-capacitor 또는 Redox capacitor), 리튬이온을 활용한 리튬이온 커패시터(Lithium ion Capacitor, LIC) 및 하이브리드 커패시터(Hybrid Capacitor, HC)로 나눌 수 있다.Electrochemical capacitors, which store and convert electrical energy using electrochemical principles, are called ultracapacitors or supercapacitors. Depending on the driving principle, the above-mentioned electrochemical capacitors are broadly divided into electric double layer capacitors (EDLC), which use activated carbon as the main electrode, and pseudo-capacitors (pseudo-capacitors or redox), which use metal oxides and conductive polymers as electrodes. capacitor), lithium ion capacitor (LIC) using lithium ions, and hybrid capacitor (HC).
초고용량 커패시터(Supercapacitor)는 전극/전해질 계면 부근의 전기이중층에서의 정전기적 인력에 의한 가역적 전하의 흡·탈착에 의해서 에너지를 저장하는 고출력 및 수명 측면에서 우수한 전기에너지 저장 장치이며 기존의 정전기식 커패시터(Electrostatic capacitor)와 비교하여 패러드(F) 이상의 고용량을 가질 수 있다.Supercapacitor is an electrical energy storage device that stores energy through reversible charge adsorption and desorption due to electrostatic attraction in the electric double layer near the electrode/electrolyte interface, and is superior in terms of high output and lifespan to conventional electrostatic capacitors. Compared to an electrostatic capacitor, it can have a higher capacity of more than a farad (F).
전기이중층 원리를 이용한 초고용량 커패시터는 활성탄 표면에 이온의 물리적인 정전기적 흡·탈착에 의해서 에너지를 저장 및 공급하는 전기화학 장치이며, 전극의 양단에 수 볼트 (2.3 ~ 3.0V)의 전압을 인가하여 전해액 내의 전극표면에 흡착되어 발생되는 전기화학적 메커니즘으로 작동될 수 있다.An ultra-high capacity capacitor using the electric double layer principle is an electrochemical device that stores and supplies energy through the physical electrostatic adsorption and desorption of ions on the surface of activated carbon, and a voltage of several volts (2.3 ~ 3.0V) is applied to both ends of the electrode. Therefore, it can be operated by an electrochemical mechanism that occurs by adsorption on the surface of the electrode in the electrolyte solution.
일반적으로 잘 알려진 리튬이차전지와 초고용량 커패시터를 비교하면 에너지 밀도는 리튬이온전지가 일반적으로 고에너지 밀도(250 ~ 300 Wh/kg)를 보이지만 초고용량 커패시터는 낮은 에너지 밀도(≤ 10 Wh/kg)에 비해 10배 이상의 고출력 밀도(< 10,000 W/kg)를 가지는 특성을 보이고 있다.When comparing the well-known lithium secondary batteries and ultra-high capacity capacitors, lithium-ion batteries generally show high energy density (250 ~ 300 Wh/kg), but ultra-high capacity capacitors have low energy density (≤ 10 Wh/kg). It has the characteristic of having a high power density (< 10,000 W/kg) that is more than 10 times higher than that of
이러한 초고용량 커패시터는 전력 밀도가 높고, 충·방전 속도가 수 초(sec)에서 수 분(min)으로 빠르게 진행된다. 초고용량 캐패시터는 주요 반응이 전하의 흡·탈착 반응으로 수명이 긴 특성을 가지고 있다. 따라서 기존의 소형기기의 온보드(On-board)용 뿐 아니라 고출력 특성이 필요한 기차나 하이브리드 버스, 전기자동차, 수소전기차 및 빠른 부하응답 특성이 요구되는 신재생에너지 발전 시스템에 적용될 수 있다.These ultra-high capacity capacitors have high power density and fast charging and discharging speeds from several seconds (sec) to several minutes (min). Ultra-high capacity capacitors have long lifespan because their main reaction is charge adsorption and desorption. Therefore, it can be applied not only to on-board existing small devices, but also to trains, hybrid buses, electric vehicles, hydrogen electric vehicles that require high output characteristics, and new and renewable energy power generation systems that require fast load response characteristics.
고전압 및 고온 환경을 요구하는 스마트 그리드 전송, 스마트 그리드 분산전원 및 스마트 그리드 운송 분야에서는 고전압 특성을 위해 단위 셀의 직렬을 통한 고전압화를 구현하고 있다. 최근 신재생에너지와 연계한 스마트 그리드 또는 스마트 씨티의 핵심 제품으로 적용되고 있는 스마트미터에도 2직렬 초고용량 커패시터가 적용되고 있다. 또한 초고용량 캐패시터는 주로 소형 제품과 리튬 일차전지를 병렬로 연결하여 사용되고 있다.In the fields of smart grid transmission, smart grid distributed power, and smart grid transportation that require high voltage and high temperature environments, high voltage is implemented through series of unit cells for high voltage characteristics. Recently, 2-series ultra-high capacity capacitors are also being applied to smart meters, which are being applied as core products of smart grids or smart cities linked to new and renewable energy. In addition, ultra-high capacity capacitors are mainly used in small products and lithium primary batteries connected in parallel.
이러한 초고용량 커패시터는 소형의 경우 2.5 ~ 3.0 V (∼400F)의 제품이 상용화 되고 있으며, 대형(1000F∼)은 2.7∼2.85V 제품이 출시되고 있어, 향후 고전압화 요구에 따라 고전압화에 따른 장기신뢰성 제품 개발이 필요하다.These ultra-high capacitance capacitors are being commercialized in small 2.5 ~ 3.0 V (~400F) products, and large 2.7 ~ 2.85V capacitors (1000F ~) are being released, which will meet the demand for higher voltage in the future. Reliable product development is necessary.
3.0 V급을 넘어서는 고전압 초고용량 커패시터가 상온 ~ 65℃의 범위에서 안정적으로 사용 가능하도록 하는 전극, 전해액 및 셀 제조방법이 요구된다.Electrode, electrolyte, and cell manufacturing methods are required to enable high-voltage ultra-high capacity capacitors exceeding the 3.0 V class to be stably used in the range of room temperature to 65°C.
고전압에 대한 내구성 및 긴 수명을 가지는 우수한 초고용량 커패시터를 제조하기 위해서는 전극성능 향상이 우선된다. In order to manufacture excellent ultra-high capacity capacitors with durability against high voltage and long lifespan, improving electrode performance is a priority.
3.0V급 셀을 65℃에서 1000h 가속 시험 후 전극 내부를 분석한 결과 주요 열화 원인은 첫째, 전극의 탈리현상이 나타나고 있으며, 알루미늄 호일과 활성탄 간의 공극이 발생하면서 저항의 주된 요인으로 나타났다. 둘째, 전극이 갈라지는 현상으로, 장시간 사용에 따른 전극 갈라짐 현상은 전자 전도성의 저하 요인으로 저항 증가 및 용량 감소 등 성능 저하로 이어질 수 있다.As a result of analyzing the inside of the electrode after a 1000h acceleration test of a 3.0V cell at 65°C, the main causes of deterioration were first, the detachment of the electrode, and the formation of voids between the aluminum foil and activated carbon, which was found to be the main cause of resistance. Second, electrode cracking occurs due to long-term use, which is a factor in reducing electronic conductivity and can lead to performance degradation such as increased resistance and reduced capacity.
고전압 3.1 V 초고용량 커패시터 셀을 제조하기 위해서는 기존 적용되던 바인더 PTFE(polytetrafluoroethylene), SBR(styrene butadiene rubber) 및 CMC(carboxymethylcellulose) 를 대신하여 가혹조건(고전압, 고온)에서 전극이 분해되는 현상 및 전극이 갈라지는 현상을 억제시켜, 셀 내구성에 영향을 주는 요인을 최소화할 수 있는 캐패시터 셀이 요구된다. In order to manufacture high-voltage 3.1 V ultra-high capacity capacitor cells, the binders PTFE (polytetrafluoroethylene), SBR (styrene butadiene rubber), and CMC (carboxymethylcellulose) that were previously applied were used to prevent electrode decomposition and electrode decomposition under harsh conditions (high voltage, high temperature). A capacitor cell that can suppress cracking and minimize factors affecting cell durability is required.
또한 불소가 치환된 아크릴계 바인더를 적용하여 고전압 환경에 적합한 전극을 제조 하거나 올레핀계 바인더를 사용하여 전극을 제조할 수 있다. 또는 해당 아크릴계 바인더와 올레핀계 바인더를 혼합한 혼합 바인더를 사용하여 전극의 탈리 현상이나 전극 자체의 갈라짐 현상을 해결하는 방안이 요구된다.Additionally, an electrode suitable for a high-voltage environment can be manufactured by applying a fluorine-substituted acrylic binder, or an olefin-based binder can be used to manufacture an electrode. Alternatively, a method of solving the detachment phenomenon of the electrode or the cracking phenomenon of the electrode itself is required by using a mixed binder that is a mixture of the corresponding acrylic binder and an olefin binder.
본 발명의 일 실시예에 따르면 양극, 음극, 분리막 및 전해액을 포함하는 전기이중층 커패시터에 있어서, 상기 양극 및 음극은 집전체 및 상기 집전체 상에 형성된 전극 활물질층을 포함하되, 상기 전극 활물질층은, 활성탄, 도전재 및 불소가 치환된 아크릴계 바인더 및 올레핀계 바인더로부터 선택되는 1종 이상의 바인더를 포함하고, 상기 전해액은, 염(salt)으로서 스파이로-(1,1')-바이피롤리디움 테트라플루오로보레이트(spiro-(1,1')-bipyrrolidium tetrafluoroborate, SBPBF4)을 포함하고, 용매로서 아세토니트릴(Acetonitrile, AN) 및 트리스(2,2,2-트리플루오로에틸) 포스파이트(Tris(2,2,2-trifluoroethyl)phosphite, TTFP)의 혼합 용매를 포함하는 고전압 및 고신뢰성 초고용량 전기이중층 커패시터가 제공된다.According to one embodiment of the present invention, in an electric double layer capacitor including an anode, a cathode, a separator, and an electrolyte, the anode and the cathode include a current collector and an electrode active material layer formed on the current collector, wherein the electrode active material layer is , activated carbon, a conductive material, and at least one binder selected from fluorine-substituted acrylic binders and olefin-based binders, and the electrolyte solution contains spiro-(1,1')-bipyrrolidium as a salt. It contains tetrafluoroborate (spiro-(1,1')-bipyrrolidium tetrafluoroborate, SBPBF 4 ), and as a solvent, acetonitrile (AN) and tris (2,2,2-trifluoroethyl) phosphite ( A high-voltage and high-reliability ultra-high capacity electric double layer capacitor containing a mixed solvent of Tris(2,2,2-trifluoroethyl)phosphite (TTFP) is provided.
또한, 고전압 및 고신뢰성 초고용량 전기이중층 커패시터의 상기 전극 활물질층은 활성탄, 도전재 및 바인더를 각각 85~90 : 5~10 : 1~5의 중량비로 포함하는 것이 바람직하다.In addition, the electrode active material layer of the high-voltage and high-reliability ultra-high capacity electric double layer capacitor preferably includes activated carbon, a conductive material, and a binder at a weight ratio of 85 to 90:5 to 10:1 to 5, respectively.
또한, 고전압 및 고신뢰성 초고용량 전기이중층 커패시터의 상기 집전체는 알루미늄 호일(aluminum foil)일 수 있으나 이에 제한되는 것은 아니다.In addition, the current collector of the high-voltage, high-reliability, ultra-high capacity electric double layer capacitor may be aluminum foil, but is not limited thereto.
또한, 고전압 및 고신뢰성 초고용량 전기이중층 커패시터의 상기 혼합 용매는 아세토니트릴 95 ~ 99 중량% 및 트리스(2,2,2-트리플루오로에틸) 포스파이트를 1 ~ 5 중량% 포함하는 것이 바람직하다.In addition, the mixed solvent of the high-voltage and high-reliability ultra-high capacity electric double layer capacitor preferably contains 95 to 99% by weight of acetonitrile and 1 to 5% by weight of tris (2,2,2-trifluoroethyl) phosphite. .
본 발명의 다른 실시예에 따라, 불소가 치환된 아크릴계 바인더 또는 올레핀계 바인더로부터 선택되는 1종 이상의 바인더, 활성탄 및 도전재를 포함하는 전극 활물질 조성물을 제조하는 단계, 상기 전극 활물질 조성물을 집전체 상에 코팅해 양극 및 음극을 각각 제조하는 단계, 아세토니트릴(Acetonitrile, AN) 및 트리스(2,2,2-트리플루오로에틸)포스파이트(Tris(2,2,2-trifluoroethyl)phosphite, TTFP)를 포함하는 혼합 용매에 스파이로-(1,1')-바이피롤리디움 테트라플루오로보레이트(spiro-(1,1')-bipyrrolidium tetrafluoroborate, SBPBF4)를 첨가하고 교반해 전해액을 제조하는 단계 및 상기 양극과 상기 음극 사이에 분리막을 배치하고 상기 양극 및 상기 음극을 상기 전해액에 함침시키는 단계를 포함하는, 고전압 및 고신뢰성 초고용량 전기이중층 커패시터의 제조방법이 제공된다.According to another embodiment of the present invention, preparing an electrode active material composition comprising at least one binder selected from a fluorine-substituted acrylic binder or an olefin-based binder, activated carbon, and a conductive material, placing the electrode active material composition on a current collector. Manufacturing the anode and cathode respectively by coating with acetonitrile (AN) and tris(2,2,2-trifluoroethyl)phosphite (TTFP) Adding spiro-(1,1')-bipyrrolidium tetrafluoroborate (SBPBF 4 ) to a mixed solvent containing and stirring to prepare an electrolyte solution. and disposing a separator between the anode and the cathode and impregnating the anode and the cathode in the electrolyte solution. A method of manufacturing a high-voltage and high-reliability ultra-high capacity electric double layer capacitor is provided.
고전압 3.1 V 초고용량 커패시터 셀을 제조하기 위해서는 기존 적용되던 바인더 PTFE, SBR, CMC 대신 가혹조건(고전압, 고온)에서 분해되는 현상 및 전극이 갈라지는 현상을 억제시켜, 셀 내구성에 영향을 주는 요인을 최소화하는 것이 필요하다. 또한 불소가 치환된 아크릴계 바인더를 적용하여 고전압 환경에 적합한 전극을 제조하거나 올레핀계 바인더를 사용한 전극을 제조할 수 있다. 또한 해당 아크릴계 바인더와 올레핀계 바인더를 혼합한 혼합 바인더를 사용하여 전극의 탈리 현상이나 전극 자체의 갈라짐 현상을 해결하는 것이 필요하다.In order to manufacture high-voltage 3.1 V ultra-high capacity capacitor cells, instead of the previously used binders PTFE, SBR, and CMC, the phenomenon of decomposition and electrode cracking under harsh conditions (high voltage, high temperature) is suppressed and factors affecting cell durability are minimized. It is necessary to do Additionally, an electrode suitable for a high-voltage environment can be manufactured by applying a fluorine-substituted acrylic binder, or an electrode using an olefin-based binder can be manufactured. In addition, it is necessary to solve the phenomenon of detachment of the electrode or cracking of the electrode itself by using a mixed binder that mixes the corresponding acrylic binder and the olefin binder.
상술한 전극의 탈리 현상 또는 전극 자체의 갈라짐 현상을 해결하기 위해서는 제조된 전극과 전해액과의 반응성이 중요하다.In order to solve the above-described phenomenon of electrode detachment or cracking of the electrode itself, the reactivity between the manufactured electrode and the electrolyte solution is important.
또한 제조된 전극과 전해액과의 반응성이 중요하며, 본 발명에서는 기존에 주로 사용되고 있는 테트라에틸암모늄 테트라플루오로보레이트(TEABF4) 염을 대신하여 스파이로-(1,1')-바이피롤리디움 테트라플루오로보레이트(spiro-(1,1')-bipyrrolidium tetrafluoroborate, SBPBF4)을 사용하고 용매는 아세토니트릴(Acetonitrile, AN)을 사용한다. In addition, the reactivity between the manufactured electrode and the electrolyte is important, and in the present invention, spiro-(1,1')-bipyrrolidium is used instead of the tetraethylammonium tetrafluoroborate (TEABF 4 ) salt that is mainly used. Tetrafluoroborate (spiro-(1,1')-bipyrrolidium tetrafluoroborate, SBPBF 4 ) is used, and acetonitrile (AN) is used as a solvent.
전해질은 염(salt)과 용매(solvent) 및 첨가제로 구성되며, 염의 경우 이온의 크기 또한 중요하여, 활성탄소의 기공에 들어갈 수 있는 적당한 크기가 요구된다.The electrolyte is composed of salt, solvent, and additives. In the case of salt, the size of the ion is also important, so an appropriate size is required to fit into the pores of activated carbon.
이온의 적당한 크기 때문에 TEABF4 염은 전하밀도가 저하되어 음이온과의 상호작용이 적어지고 이로인해 해리도가 높지만 고전압 및 고온 구현 등 고신뢰성 제품에 적용이 어려운 문제가 있다.Due to the appropriate size of the ion, TEABF 4 salt has a lower charge density and less interaction with anions, which results in a higher degree of dissociation, but it is difficult to apply to high-reliability products such as high voltage and high temperature implementation.
용매로 사용되는 아세토니트릴(Acetonitrile, AN)은 전도도가 우수하여 주로 사용되고 있으나 끊는점이 81 ~ 82℃ 로 상대적으로 고온에 노출시 가스발생의 문제점에 노출될 수 있다. 본 발명의 일 실시예에 따르면 끊는점이 높아 온도특성이 우수한 술포란(Sulfolane, 끊는점 285℃) 및 안정성 및 난연성이 우수하고 타 첨가제와 혼합에 따른 난연성 효과가 우수한 트리스(2,2,2-트리플루오로에틸) 포스파이트(TTFP, Tris (2,2,2 - trifluoroethyl) phosphite)를 첨가하여 전해액을 구성할 수 있다.Acetonitrile (AN), which is used as a solvent, is mainly used because of its excellent conductivity, but its boiling point is 81 to 82°C, so it can be exposed to the problem of gas generation when exposed to relatively high temperatures. According to one embodiment of the present invention, sulfolane (boiling point 285°C), which has excellent temperature characteristics due to its high boiling point, and tris (2,2,2-), which has excellent stability and flame retardancy and excellent flame retardant effect when mixed with other additives The electrolyte solution can be formed by adding trifluoroethyl) phosphite (TTFP, Tris (2,2,2 - trifluoroethyl) phosphite).
본 발명의 일 실시예에 따르면 불소가 치환된 아크릴계 바인더 또는 올레핀계 바인더를 사용하여 전극을 제조하므로 전극의 탈리 현상이나 전극 자체의 갈라짐 현상을 최소화 할 수 있다. 또한 일 실시예에 따르면 전해액에 난연성 효과가 우수한 물질을 첨가하여 고전압 및 고온에 적응할 수 있는 고신뢰성 캐패시터를 생산할 수 있다.According to one embodiment of the present invention, since the electrode is manufactured using a fluorine-substituted acrylic binder or an olefin binder, the detachment phenomenon of the electrode or the cracking phenomenon of the electrode itself can be minimized. Additionally, according to one embodiment, a highly reliable capacitor adaptable to high voltage and temperature can be produced by adding a material with excellent flame retardant effect to the electrolyte solution.
도 1은 본 발명의 비교예 1, 실시예 1, 실시예 2 및 실시예 3에 따른 순환전압전류 비교 그래프이다.
도 2는 본 발명의 비교예 1, 실시예 1, 실시예 2 및 실시예 3에 따른 임피던스 비교 그래프이다.
도 3은 본 발명의 비교예 1, 실시예 1, 실시예 2 및 실시예 3에 대하여 65℃에서 1000시간 동안 용량변화율을 비교한 그래프이다.Figure 1 is a graph comparing cyclic voltage and current according to Comparative Example 1, Example 1, Example 2, and Example 3 of the present invention.
Figure 2 is an impedance comparison graph according to Comparative Example 1, Example 1, Example 2, and Example 3 of the present invention.
Figure 3 is a graph comparing the capacity change rate at 65°C for 1000 hours for Comparative Example 1, Example 1, Example 2, and Example 3 of the present invention.
본 발명의 실시예들을 설명함에 있어서, 본 발명과 관련된 공지기술에 대한 구체적인 설명이 본 발명의 요지를 불필요하게 흐릴 수 있다고 판단되는 경우에는 그 상세한 설명을 생략하기로 한다. 그리고, 후술되는 용어들은 본 발명에서의 기능을 고려하여 정의된 용어들로서 이는 사용자, 운용자의 의도 또는 관례 등에 따라 달라질 수 있다. 그러므로 그 정의는 본 명세서 전반에 걸친 내용을 토대로 내려져야 할 것이다. 상세한 설명에서 사용되는 용어는 단지 본 발명의 실시예들을 기술하기 위한 것이며, 결코 제한적으로 해석되어서는 안 된다. 명확하게 달리 사용되지 않는 한, 단수 형태의 표현은 복수 형태의 의미를 포함한다. 본 설명에서, "포함" 또는 "구비"와 같은 표현은 어떤 특성들, 숫자들, 단계들, 동작들, 요소들, 이들의 일부 또는 조합을 가리키기 위한 것이며, 기술된 것 이외에 하나 또는 그 이상의 다른 특성, 숫자, 단계, 동작, 요소, 이들의 일부 또는 조합의 존재 또는 가능성을 배제하는 것으로 해석되어서는 안 된다.In describing the embodiments of the present invention, if it is determined that a detailed description of the known technology related to the present invention may unnecessarily obscure the gist of the present invention, the detailed description will be omitted. In addition, the terms described below are terms defined in consideration of functions in the present invention, and may vary depending on the intention or custom of the user or operator. Therefore, the definition should be made based on the contents throughout this specification. The terms used in the detailed description are merely for describing embodiments of the present invention and should in no way be construed as limiting. Unless explicitly stated otherwise, singular forms include plural meanings. In this description, expressions such as “comprising” or “comprising” are intended to indicate certain features, numbers, steps, operations, elements, parts or combinations thereof, and one or more than those described. It should not be construed to exclude the existence or possibility of any other characteristic, number, step, operation, element, or part or combination thereof.
이하, 도면을 참조하여 본 발명의 구체적인 실시형태를 설명하기로 한다. 이하의 상세한 설명은 본 명세서에서 기술된 방법, 장치 및/또는 시스템에 대한 포괄적인 이해를 돕기 위해 제공된다. 그러나 이는 예시에 불과하며 본 발명은 이에 제한되지 않는다.Hereinafter, specific embodiments of the present invention will be described with reference to the drawings. The detailed description below is provided to provide a comprehensive understanding of the methods, devices and/or systems described herein. However, this is only an example and the present invention is not limited thereto.
1. 전해액 제조1. Electrolyte preparation
[비교예 1] 1.0M SBPBF4 / AN 제작[Comparative Example 1] Production of 1.0M SBPBF 4 / AN
SBPBF4을 용질로 AN을 용매로 사용하여 1.0M로 제조하였다. 이때 전해액 내 수분 함량을 30 ppm 이하로 관리하였다.SBPBF 4 was prepared at 1.0M using AN as the solute and AN as the solvent. At this time, the moisture content in the electrolyte was controlled to 30 ppm or less.
[실시예 1] 1.0M SBPBF4 / AN : TTFP (99 wt.% : 1 wt.%) 제작[Example 1] Production of 1.0M SBPBF 4 / AN: TTFP (99 wt.%: 1 wt.%)
SBPBF4을 용질로 AN : TTFP 를 99 : 1 wt.% 로 혼합하여 혼합된 용매를 사용하여 1.0M로 제조하였다. 이때 전해액 내 수분 함량을 30 ppm 이하로 관리하였다.SBPBF 4 was prepared by mixing AN:TTFP at 99:1 wt.% as the solute and using the mixed solvent to make 1.0M. At this time, the moisture content in the electrolyte was controlled to 30 ppm or less.
[실시예 2] 1.0M SBPBF4 / AN : TTFP (97 wt.% : 3 wt.%) 제작[Example 2] Production of 1.0M SBPBF 4 / AN: TTFP (97 wt.%: 3 wt.%)
SBPBF4을 용질로 AN : TTFP 를 97 : 3 wt.% 로 혼합하여 혼합된 용매를 사용하여 1.0M로 제조하였다. 이때 전해액 내 수분 함량을 30 ppm 이하로 관리하였다.SBPBF 4 was prepared by mixing AN:TTFP at 97:3 wt.% as the solute and using the mixed solvent to make 1.0M. At this time, the moisture content in the electrolyte was controlled to 30 ppm or less.
[실시예 3] 1.0M SBPBF4 / AN : TTFP (95 wt.% : 5 wt.%) 제작[Example 3] Production of 1.0M SBPBF 4 / AN: TTFP (95 wt.%: 5 wt.%)
SBPBF4을 용질로 AN : TTFP 를 95 : 5 wt.% 로 혼합하여 혼합된 용매를 사용하여 1.0M로 제조하였다. 이때 전해액 내 수분 함량을 30 ppm 이하로 관리하였다.SBPBF 4 was prepared by mixing AN:TTFP at 95:5 wt.% as the solute and using the mixed solvent to make 1.0M. At this time, the moisture content in the electrolyte was controlled to 30 ppm or less.
1. 초고용량 커패시터 제조1. Manufacturing ultra-high capacity capacitors
본 발명에 사용된 주 전극 활물질인 활성탄소를 전처리(350 ~ 450 ℃, 질소(N2) 조건에서 2시간 이상) 하여 사용하였으며, 이때 활성탄 : 도전재 : 바인더 = 85~90 : 5~10 : 1~5 wt.%으로 혼합하여 제조한 슬러리액을 알루미늄 호일(Al Foil)에 코팅 및 롤 프레스(Roll Press)하여 양극 및 음극으로 사용되는 활성탄 전극을 제조하였다. 도전재는 카본블랙, 바인더는 불소가 치환된 아크릴계 또는 올레핀계를 사용하였다.Activated carbon, the main electrode active material used in the present invention, was used after pretreatment (350 ~ 450 ℃, for more than 2 hours under nitrogen (N 2 ) conditions), where activated carbon: conductive material: binder = 85 ~ 90: 5 ~ 10: The slurry solution prepared by mixing 1 to 5 wt.% was coated on aluminum foil and rolled pressed to produce activated carbon electrodes used as anodes and cathodes. Carbon black was used as the conductive material, and fluorine-substituted acrylic or olefin-based binder was used.
일 실시예에 따르면 불소가 치환된 아크릴계 바인더는 메틸아크릴레이트(methyl acrylate), 메틸(메타)아크릴레이트(methylmethacrylate), 트리메틸올프로판트리아크릴레이트(trimethylolpropanetriacrylate), 에틸아크릴레이트(ethyl acrylate), 에틸시야노아크릴레이트(ethylcyanoacrylate), 뷰틸아크릴레이트(butylacrylate), 뷰틸메타아크릴레이트(butyl methacrylate), 하이드록시에틸메타아크릴레이트(hydroxyethyl methacrylate), 바이닐아세테이트(vinylacetate), 아크릴로나이트릴(acrylonitrile), 펜타에리스리톨 트리아크릴레이트(pentaerythritol tetraacrylate), 하이드록시에틸메타크릴레이트(hydroxyethyl methacrylate) 로 주어진 군에서 선택된 1종 또는 2종 화합물에서 불소가 치환된 화합물로 제조된 바인더일 수 있다.According to one embodiment, the fluorine-substituted acrylic binder is methyl acrylate, methyl (meth)acrylate, trimethylolpropanetriacrylate, ethyl acrylate, and ethyl acrylate. Ethylcyanoacrylate, butylacrylate, butyl methacrylate, hydroxyethyl methacrylate, vinylacetate, acrylonitrile, pentaerythritol It may be a binder manufactured from a compound in which fluorine is substituted in one or two compounds selected from the group given as triacrylate (pentaerythritol tetraacrylate) and hydroxyethyl methacrylate.
일 실시예에 따르면 올레핀계 바인더는 폴리에틸렌(polyethylene), 폴리프로필렌(polypropylene), 폴리테트라플루오르 에틸렌(polytetrafluoroethylene), 에틸렌 프로필렌 다이엔 모노모 러버(ethylene propylene diene monomer rubber), 폴리에틸렌다이옥시티오펜(poly(3,4-ethylenedioxy-thiophene)), 폴리에틸렌이민(polyethyleneimine), 폴리에틸렌 글리콜(polyethylene glycols), 폴리에틸렌옥사이드(polyethylene oxide) 중에서 선택된 화합물로 제조된 바인더일 수 있다.According to one embodiment, the olefin-based binder is polyethylene, polypropylene, polytetrafluoroethylene, ethylene propylene diene monomer rubber, and polyethylene dioxythiophene (poly( It may be a binder made of a compound selected from 3,4-ethylenedioxy-thiophene), polyethyleneimine, polyethylene glycols, and polyethylene oxide.
올레핀계 바인더 적용 제조 공정은 먼저 활성탄소와 도전재를 건조 상태로 믹싱을 하여 충분히 혼합한다. 본 발명에서 사용되는 바인더는 별도로 혼합된 물질을 사용하며 혼합 비율은 투입되는 양을 5 wt.%로 가정했을 때, 올레핀계 바인더 2.5 ~ 3.5 wt.%, CMC 0.5 ~ 1.5 wt.%, PVP 0.1 ~ 0.3 wt.%로 조절하여 초순수에 용해하여 제조한다. 올레핀계 바인더의 함량이 과할 경우 전극 결착력은 좋아지지만 저항 및 성능에 영향을 줄 수 있다. CMC(carboxymethylcellulose) 함량이 부족할 경우 전극이 혼합되지 않고 응집되는 현상이 발생할 수 있다. PVP(polyvinylpyrrolidone)는 분산재로 최대한 다른 바인더에 분산성 이외에는 영향을 주지 않는 범위내에서 사용할 수 있다. 본 발명의 일 실시예에 따르면 전극의 최적화를 위하여 불소가 치환된 아크릴계 바인더 또는 올레핀계 바인더를 사용할 수 있다. 또는 해당 아크릴계 바인더 및 올레핀계 바인더를 혼합한 혼합 바인더를 사용할 수 있다.In the manufacturing process of applying an olefin binder, the activated carbon and the conductive material are first mixed in a dry state and thoroughly mixed. The binder used in the present invention uses separately mixed materials, and the mixing ratio is 2.5 to 3.5 wt.% of olefinic binder, 0.5 to 1.5 wt.% of CMC, and 0.1 wt.% of PVP, assuming the input amount is 5 wt.%. It is prepared by adjusting to ~0.3 wt.% and dissolving in ultrapure water. If the content of olefin-based binder is excessive, electrode bonding strength improves, but resistance and performance may be affected. If the CMC (carboxymethylcellulose) content is insufficient, a phenomenon in which the electrodes do not mix and agglomerate may occur. PVP (polyvinylpyrrolidone) is a dispersant that can be used as long as it does not affect other binders other than dispersibility. According to one embodiment of the present invention, a fluorine-substituted acrylic binder or an olefin binder can be used to optimize the electrode. Alternatively, a mixed binder that mixes the corresponding acrylic binder and olefin binder can be used.
건조 상태로 믹싱한 활성탄소 및 도전재를 초순수에 첨가하여 믹싱 후 바인더를 첨가하고 믹싱하여 전극 활물질을 제조한다. 전극 활물질 제조 후 알루미늄 호일에 코팅하여 최종 전극을 제조한다. Activated carbon and conductive material mixed in a dry state are added to ultrapure water, mixed, then a binder is added and mixed to prepare an electrode active material. After manufacturing the electrode active material, the final electrode is manufactured by coating it on aluminum foil.
초고용량 캐패시터는 라디알(원통형) 타입(형태)으로 제작, 분리막을 기준으로 양쪽에 전극을 위치하여 권취형으로 소자를 말아 제조하였다. 이와 같이 제조된 소자의 수분을 제거하기 위하여, 130℃에서 48시간 동안 건조한다.The ultra-high capacity capacitor was manufactured in a radial (cylindrical) type (shape), with electrodes placed on both sides of the separator and rolled into a coiled device. To remove moisture from the device manufactured in this way, it is dried at 130°C for 48 hours.
그리고 건조된 소자를 상기에서 제조된 전해액(비교예 1, 실시예 1, 2, 3)를 각각 사용하여 함침한 뒤, 소자를 알루미늄 캔(크기: D80 x L20 mm)에 넣어 원통형 셀로 제작하였다. 이때, 건조부터 알루미늄 캔에 넣어 셀로 제작할 때까지 수분이 30 ppm 이하로 유지되는 드라이룸 안에서 제조하였다.Then, the dried device was impregnated using the electrolyte solution prepared above (Comparative Example 1, Examples 1, 2, and 3), and then the device was placed in an aluminum can (size: D80 x L20 mm) to make a cylindrical cell. At this time, it was manufactured in a dry room where the moisture was maintained below 30 ppm from drying to manufacturing into cells in aluminum cans.
2. 초고용량 커패시터 평가2. Evaluation of ultra-high capacitance capacitors
[평가 1] 온도별 순환전압전류법(Cyclic voltammetry) 평가 : 전기화학적 특성 평가[Evaluation 1] Cyclic voltammetry evaluation by temperature: electrochemical property evaluation
Cyclic voltammetry 평가를 위해 25℃에서 Cyclic voltammetry를 이용하여 측정하였으며, 그때 주사속도는 50 mV/s로 고정하였으며, 전압은 0 ~ 3.1V 영역에서 측정하였다. 측정 조건은 하기의 표 1과 같다.To evaluate cyclic voltammetry, measurements were made using cyclic voltammetry at 25°C. At that time, the scanning speed was fixed at 50 mV/s, and the voltage was measured in the range of 0 to 3.1V. The measurement conditions are shown in Table 1 below.
[평가 2] 임피던스(AC Impedance) 평가 : 전기화학적 특성 평가[Evaluation 2] Impedance (AC Impedance) evaluation: Electrochemical characteristics evaluation
임피던스 평가를 위해 25℃에서 AC 임피던스 법을 이용하여 측정하였으며, 그때 주파수 범위는 100 kHz ~ 10mHz 영역에서 측정하였다.For impedance evaluation, measurements were made using the AC impedance method at 25°C, and the frequency range was measured in the range of 100 kHz to 10 mHz.
[평가 3] 고온 장기 신뢰성 평가[Evaluation 3] High temperature long-term reliability evaluation
고온 장기 신뢰성 평가를 진행하기 위해 초기성능평가를 위해 제조된 각 셀을 충전/방전을 실시하여 초기용량(Capacitance, F), DC-ESR을 측정하였으며, 이때 충전/방전 전류는 50 mA로 평가하였다. 이후 65℃의 항온챔버 안에서 3.1V로 정전류로 충전하였으며, 각 시간에 따라 셀을 온장고 안에서 꺼내어 실온에서 30분 정도 보관하여 셀의 열 평준화를 시킨 후, 변화된 용량을 비교하였다.In order to conduct high-temperature long-term reliability evaluation, each cell manufactured for initial performance evaluation was charged/discharged and initial capacity (F) and DC-ESR were measured, and the charge/discharge current was evaluated at 50 mA. . Afterwards, it was charged with a constant current of 3.1V in a constant temperature chamber at 65°C. At each time, the cell was taken out of the refrigerator and stored at room temperature for about 30 minutes to equalize the heat of the cell, and then the changed capacity was compared.
도 1은 본 발명의 비교예 1, 실시예 1, 실시예 2 및 실시예 3에 따른 순환전압전류 비교 그래프이다. 도 1을 참조하면 비교예 1, 실시예 1, 2, 3에 따라 전기화학적 특성을 비교하기 위해 순환전압전류법을 통하여 실시한 후 비교한 결과 비교예 1과 큰 차이가 없음을 확인하였다. 본 발명의 일 실시예에 따른 전해액 조성 변화가 단기적으로는 캐패시터의 성능 변화를 주지 않음을 확인하였다.Figure 1 is a graph comparing cyclic voltage and current according to Comparative Example 1, Example 1, Example 2, and Example 3 of the present invention. Referring to Figure 1, cyclic voltammetry was performed to compare the electrochemical properties according to Comparative Example 1 and Examples 1, 2, and 3, and as a result of comparison, it was confirmed that there was no significant difference from Comparative Example 1. It was confirmed that changes in electrolyte composition according to an embodiment of the present invention did not change the performance of the capacitor in the short term.
3.1V까지 변화를 확인한 결과 전형적인 전기이증층에 따른 곡선을 나타내고 있으며 이상반응(예: 가스발생, 분해반응 등에 의한 전류의 급격한 상승 변화)이 발견되지 않았다. 안정적인 초고용량 커패시터 구동을 위해서는 급격한 전류의 상승변화등이 없어야 한다.As a result of checking the change up to 3.1V, it shows a curve according to a typical electric surge layer, and no abnormal reactions (e.g., sudden increase in current due to gas generation, decomposition reaction, etc.) were found. In order to drive a stable ultra-high capacity capacitor, there should be no sudden rise or change in current.
도 2는 본 발명의 비교예 1, 실시예 1, 실시예 2 및 실시예 3에 따른 임피던스 비교 그래프이다. 도 2를 참조하면 비교예 1, 실시예 1, 2, 3에 따라 전기화학적 특성을 비교하기 위해 임피던스법을 통하여 성능 평가를 실시한 후 비교한 결과를 볼 수 있다. 비교예 1과 비교하여 실시예 3의 경우 1 ~ 2 mΩ 정도의 전해액 저항 감소가 이루어졌음을 확인하였다(가로축 저항). 전체적으로 확산 저항을 가르키는 상승 곡선은 큰 차이를 보이고 있지 않음을 확인하였다. 순환전압전류법에서도 나타나듯이 전해액 조성 변화가 단기적으로는 변화를 주지 않음을 확인하였다.Figure 2 is an impedance comparison graph according to Comparative Example 1, Example 1, Example 2, and Example 3 of the present invention. Referring to FIG. 2, you can see the results of performance evaluation after performance evaluation through impedance method to compare electrochemical properties according to Comparative Example 1 and Examples 1, 2, and 3. Compared to Comparative Example 1, it was confirmed that the electrolyte resistance was reduced by about 1 to 2 mΩ in Example 3 (horizontal resistance). Overall, it was confirmed that the rising curve indicating diffusion resistance did not show a significant difference. As shown in cyclic voltammetry, it was confirmed that changes in electrolyte composition did not cause changes in the short term.
도 3은 본 발명의 비교예 1, 실시예 1, 실시예 2 및 실시예 3에 대하여 65℃에서 1000시간 동안 용량변화율을 비교한 그래프이다. 도 3을 참조하면 비교예 1, 실시예 1, 2, 3에 따라 용량변화율을 확인한 결과 비교예 1에 비해서 실시예 2, 3의 용량유지율이 7 ~ 8% 우수한 것을 확인하였다. 이러한 차이는 장기적으로 사이클 수명에 큰 영향을 줄 수 있다. 일반적으로 65℃에서 안정적으로 초고용량 커패시터가 작동되는 것을 확인하기 위해서 1000시간 후 용량변화율이 70%이내여야 한다. 이로서 본 발명에 따른 캐패시터는 전극의 탈리 현상이나 전극 자체의 갈라짐 현상이 최소화되고 또한 고전압 및 고온에 적응할 수 있는 고신뢰성 캐패시터임을 확인할 수 있었다.Figure 3 is a graph comparing the capacity change rate for Comparative Example 1, Example 1, Example 2, and Example 3 of the present invention at 65°C for 1000 hours. Referring to Figure 3, as a result of checking the capacity change rate according to Comparative Example 1 and Examples 1, 2, and 3, it was confirmed that the capacity retention rate of Examples 2 and 3 was 7 to 8% superior to Comparative Example 1. These differences can have a significant impact on cycle life in the long term. Generally, in order to confirm that an ultra-high capacity capacitor operates stably at 65°C, the capacity change rate must be within 70% after 1000 hours. As a result, it was confirmed that the capacitor according to the present invention minimizes the phenomenon of electrode detachment or cracking of the electrode itself, and is a highly reliable capacitor that can adapt to high voltage and high temperature.
전술한 본 발명의 설명은 예시를 위한 것이며, 본 발명이 속하는 기술분야의 통상의 지식을 가진 자는 본 발명의 기술적 사상이나 필수적인 특징을 변경하지 않고서 다른 구체적인 형태로 쉽게 변형이 가능하다는 것을 이해할 수 있을 것이다. 그러므로 이상에서 기술한 실시예들은 모든 면에서 예시적인 것이며 한정적이 아닌 것으로 이해해야만 한다.The description of the present invention described above is for illustrative purposes, and those skilled in the art will understand that the present invention can be easily modified into other specific forms without changing the technical idea or essential features of the present invention. will be. Therefore, the embodiments described above should be understood in all respects as illustrative and not restrictive.
본 발명의 범위는 상기 상세한 설명보다는 후술하는 특허청구범위에 의하여 나타내어지며, 특허청구범위의 의미 및 범위 그리고 그 균등 개념으로부터 도출되는 모든 변경 또는 변형된 형태가 본 발명의 범위에 포함되는 것으로 해석되어야 한다.The scope of the present invention is indicated by the claims described below rather than the detailed description above, and all changes or modified forms derived from the meaning and scope of the claims and their equivalent concepts should be construed as being included in the scope of the present invention. do.
Claims (5)
상기 양극 및 음극은 집전체 및 상기 집전체 상에 형성된 전극 활물질층을 포함하되,
상기 전극 활물질층은, 활성탄; 도전재; 및 불소가 치환된 아크릴계 바인더와 올레핀계 바인더의 혼합 바인더; 를 포함하고,
상기 전해액은, 염(salt)으로서 스파이로-(1,1')-바이피롤리디움 테트라플루오로보레이트(spiro-(1,1')-bipyrrolidium tetrafluoroborate, SBPBF4)을 포함하고, 용매로서 아세토니트릴(Acetonitrile, AN) 및 트리스(2,2,2-트리플루오로에틸) 포스파이트(Tris(2,2,2-trifluoroethyl)phosphite, TTFP)의 혼합 용매를 포함하며,
상기 불소가 치환된 아크릴계 바인더는 메틸아크릴레이트(methyl acrylate), 메틸(메타)아크릴레이트(methylmethacrylate), 트리메틸올프로판트리아크릴레이트(trimethylolpropanetriacrylate), 에틸아크릴레이트(ethyl acrylate), 에틸시야노아크릴레이트(ethylcyanoacrylate), 뷰틸아크릴레이트(butylacrylate), 뷰틸메타아크릴레이트(butyl methacrylate), 하이드록시에틸메타아크릴레이트(hydroxyethyl methacrylate), 바이닐아세테이트(vinylacetate), 아크릴로나이트릴(acrylonitrile), 펜타에리스리톨 트리아크릴레이트(pentaerythritol tetraacrylate), 하이드록시에틸메타크릴레이트(hydroxyethyl methacrylate) 로 주어진 군에서 선택된 1종 또는 2종 화합물에서 불소가 치환된 화합물로 제조된 바인더인 것을 특징으로 하는,
고전압 및 고신뢰성 초고용량 전기이중층 커패시터.
anode; cathode; separation membrane; and electrolyte; In the electric double layer capacitor containing,
The positive and negative electrodes include a current collector and an electrode active material layer formed on the current collector,
The electrode active material layer includes activated carbon; conductive materials; and a mixed binder of a fluorine-substituted acrylic binder and an olefin-based binder; Including,
The electrolyte solution contains spiro-(1,1')-bipyrrolidium tetrafluoroborate (SBPBF 4 ) as a salt, and aceto as a solvent. Contains a mixed solvent of nitrile (Acetonitrile, AN) and Tris(2,2,2-trifluoroethyl)phosphite (TTFP),
The fluorine-substituted acrylic binder includes methyl acrylate, methyl (meth)acrylate, trimethylolpropanetriacrylate, ethyl acrylate, and ethylcyanoacrylate ( ethylcyanoacrylate, butylacrylate, butyl methacrylate, hydroxyethyl methacrylate, vinyl acetate, acrylonitrile, pentaerythritol triacrylate ( Characterized in that it is a binder manufactured from a compound in which fluorine is substituted in one or two compounds selected from the group given as pentaerythritol tetraacrylate) and hydroxyethyl methacrylate,
High-voltage and high-reliability ultra-high capacity electric double layer capacitor.
상기 전극 활물질층은,
활성탄, 도전재 및 바인더를 각각 85~90 : 5~10 : 1~5의 중량비로 포함하는 것을 특징으로 하는,
고전압 및 고신뢰성 초고용량 전기이중층 커패시터.
According to paragraph 1,
The electrode active material layer is,
Characterized in that it contains activated carbon, a conductive material, and a binder in a weight ratio of 85 to 90:5 to 10:1 to 5, respectively.
High-voltage and high-reliability ultra-high capacity electric double layer capacitor.
상기 집전체는 알루미늄 호일(aluminum foil)인 것을 특징으로 하는,
고전압 및 고신뢰성 초고용량 전기이중층 커패시터.
According to paragraph 1,
The current collector is characterized in that it is aluminum foil,
High-voltage and high-reliability ultra-high capacity electric double layer capacitor.
상기 혼합 용매는,
아세토니트릴 95 ~ 99 중량% 및 트리스(2,2,2-트리플루오로에틸) 포스파이트를 1 ~ 5 중량% 포함하는 것을 특징으로 하는,
고전압 및 고신뢰성 초고용량 전기이중층 커패시터.
According to paragraph 1,
The mixed solvent is,
Characterized in that it contains 95 to 99% by weight of acetonitrile and 1 to 5% by weight of tris (2,2,2-trifluoroethyl) phosphite,
High-voltage and high-reliability ultra-high capacity electric double layer capacitor.
불소가 치환된 아크릴계 바인더와 올레핀계 바인더의 혼합 바인더, 활성탄 및 도전재를 포함하는 전극 활물질 조성물을 제조하는 단계;
상기 전극 활물질 조성물을 집전체 상에 코팅해 양극 및 음극을 각각 제조하는 단계;
아세토니트릴(Acetonitrile, AN) 및 트리스(2,2,2-트리플루오로에틸)포스파이트(Tris(2,2,2-trifluoroethyl)phosphite, TTFP)를 포함하는 혼합 용매에 스파이로-(1,1')-바이피롤리디움 테트라플루오로보레이트(spiro-(1,1')-bipyrrolidium tetrafluoroborate, SBPBF4)를 첨가하고 교반해 전해액을 제조하는 단계; 및
상기 양극과 상기 음극 사이에 분리막을 배치하고 상기 양극 및 상기 음극을 상기 전해액에 함침시키는 단계; 를 포함하고,
상기 불소가 치환된 아크릴계 바인더는 메틸아크릴레이트(methyl acrylate), 메틸(메타)아크릴레이트(methylmethacrylate), 트리메틸올프로판트리아크릴레이트(trimethylolpropanetriacrylate), 에틸아크릴레이트(ethyl acrylate), 에틸시야노아크릴레이트(ethylcyanoacrylate), 뷰틸아크릴레이트(butylacrylate), 뷰틸메타아크릴레이트(butyl methacrylate), 하이드록시에틸메타아크릴레이트(hydroxyethyl methacrylate), 바이닐아세테이트(vinylacetate), 아크릴로나이트릴(acrylonitrile), 펜타에리스리톨 트리아크릴레이트(pentaerythritol tetraacrylate), 하이드록시에틸메타크릴레이트(hydroxyethyl methacrylate) 로 주어진 군에서 선택된 1종 또는 2종 화합물에서 불소가 치환된 화합물로 제조된 바인더인 것을 특징으로 하는,
고전압 및 고신뢰성 초고용량 전기이중층 커패시터의 제조방법.
In the method of manufacturing the high-voltage and high-reliability ultra-high capacity electric double layer capacitor according to claim 1,
Preparing an electrode active material composition including a mixed binder of a fluorine-substituted acrylic binder and an olefin-based binder, activated carbon, and a conductive material;
manufacturing a positive electrode and a negative electrode, respectively, by coating the electrode active material composition on a current collector;
Spiro-(1, Preparing an electrolyte solution by adding 1')-bipyrrolidium tetrafluoroborate (SBPBF 4 ) and stirring; and
Placing a separator between the anode and the cathode and impregnating the anode and the cathode into the electrolyte solution; Including,
The fluorine-substituted acrylic binder includes methyl acrylate, methyl (meth)acrylate, trimethylolpropanetriacrylate, ethyl acrylate, and ethylcyanoacrylate ( ethylcyanoacrylate, butylacrylate, butyl methacrylate, hydroxyethyl methacrylate, vinyl acetate, acrylonitrile, pentaerythritol triacrylate ( Characterized in that it is a binder manufactured from a compound in which fluorine is substituted in one or two compounds selected from the group given as pentaerythritol tetraacrylate) and hydroxyethyl methacrylate,
Manufacturing method of high-voltage and high-reliability ultra-high capacity electric double layer capacitor.
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