KR20100035870A - Gel-type electrolyte composition for electric double layer capacitors, method of preparing the same, and electric double layer capacitors comprising electrolyte layer - Google Patents
Gel-type electrolyte composition for electric double layer capacitors, method of preparing the same, and electric double layer capacitors comprising electrolyte layer Download PDFInfo
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- KR20100035870A KR20100035870A KR1020080095241A KR20080095241A KR20100035870A KR 20100035870 A KR20100035870 A KR 20100035870A KR 1020080095241 A KR1020080095241 A KR 1020080095241A KR 20080095241 A KR20080095241 A KR 20080095241A KR 20100035870 A KR20100035870 A KR 20100035870A
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- electrolyte
- electric double
- double layer
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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
- H01G11/56—Solid electrolytes, e.g. gels; Additives therein
-
- 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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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
Description
본 발명은 전기 이중층 캐패시터의 저항 증가 및 용량 감소 등의 단점을 막을 수 있으며, 액상 전해액의 태생적인 불량인 누액 불량을 원천적으로 방지할 수 있는 전기 이중층 캐패시터용 겔상 전해질 조성물과 이의 제조방법, 및 상기 조성물로부터 제조된 전해질을 포함하는 전기 이중층 캐패시터에 관한 것이다.The present invention can prevent the disadvantages such as increased resistance and reduced capacity of the electric double layer capacitor, and the gel electrolyte composition for an electric double layer capacitor and a method of manufacturing the same, which can prevent the leakage of leakage, which is a natural defect of the liquid electrolyte, and the above An electric double layer capacitor comprising an electrolyte prepared from the composition.
최근 반도체 산업에서 기술의 고도화 및 미세화 추세에 따라 초소형 정밀 기계 부품 소자와 같은 미세 소자의 제작을 위한 마이크로 공정 기술 및 재료 개발이 세계적으로 급격하게 진행되고 있다. 마이크로 공정 기술과 재료 기술의 발전에 의하여 전자, 통신용 부품은 더욱더 소형화 및 정밀화되고 있으며, 특히 기능을 갖는 부분과 이 부분을 제어하는 주변회로의 단일칩(on-chip)화의 요구가 증가되기 시작하였다. Recently, in the semiconductor industry, micro process technology and materials development for the fabrication of micro devices such as micro precision mechanical component devices are rapidly progressing in accordance with the trend of technology advancement and miniaturization. Due to the development of micro process technology and material technology, electronic and communication parts are becoming smaller and more precise, and in particular, the demand for the on-chip of parts having functions and peripheral circuits controlling these parts starts to increase. It was.
이와 같은 추세에 있어서 소형 정밀 소자의 구동을 위한 에너지원의 개발이 요구되고 있다. 즉, 소자의 크기가 작아지므로 소형의 전지가 필요하게 된 것이다. 따라서, 보다 완벽한 소형 정밀 소자의 구현을 위하여 고성능의 소형 전지의 개발이 필수적이다.In this trend, development of an energy source for driving a small precision device is required. In other words, the size of the device is small, so a small battery is required. Therefore, it is essential to develop a small battery of high performance in order to implement a more compact small precision device.
이러한 요구 조건에 가장 잘 부합되는 소형 동력원이 박막형 전지라 할 수 있다. 현재의 박막기술 및 마이크로 공정 기술을 응용하여 경량의 고성능 박막형 전지를 제작한다면 상기 요구 조건을 만족할 수 있게 된다.The smallest power source that best meets these requirements is a thin-film battery. If the current thin film technology and micro process technology are applied to produce a lightweight, high performance thin film battery, the above requirements can be satisfied.
한편, 전기화학 캐패시터(electrochemical capacitor)는 종래의 정전 캐패시터(electrostatic capacitor)에 비하여 비축전 용량(specific capacitance: F/g)이 100 ~ 1000배 이상 향상되어 슈퍼 캐패시터로 불리운다. 슈퍼 캐패시터는 2차전지에 비하여 전력 밀도가 높고, 사이클 수명이 길며, 방전율도 높고, 기타 여러가지 장점을 갖는다. 전기 자동차나 핸드폰 등의 장치에 시용되는 연료전지를 포함하는 각종 전기소자는 점점 고용량, 고효율화 되면서 높은 파워를 필요로 하고 있다. 또한 장치의 초기 온(ON), 오프(Off)시 더 많은 파워가 필요하므로 슈퍼 캐패시터를 집적화하여 일체화시킬 필요가 있다.On the other hand, the electrochemical capacitor (electrochemical capacitor) is compared with the conventional electrostatic capacitor (electrostatic capacitor) (specific capacitance (F / g)) is improved by 100 to 1000 times or more is called a super capacitor. Supercapacitors have higher power density, longer cycle life, higher discharge rate, and many other advantages over secondary batteries. Various electric devices including fuel cells used in devices such as electric vehicles and mobile phones are increasingly required for high capacity and high efficiency. In addition, since more power is required when the device is initially turned on and off, it is necessary to integrate and integrate a supercapacitor.
기존의 슈퍼 캐패시터는 전해질로써 수용액인 NaOH, H2SO4, KOH 등을 사용하는 수용액상 슈퍼 캐패시터로서 이들은 연료전지 등과 하이브리드시 이동의 불편함과 누액의 방출 등 일체화시켰을 때의 문제점을 가지고 있다. 따라서 이러한 수용액상에서의 슈퍼 캐패시터로는 상기와 같은 전해질 및 전극공정에 있어서의 공정의 집적화와 단순화는 물론 소형화가 불가능한 실정이다.Conventional supercapacitors are aqueous phase supercapacitors that use aqueous solutions of NaOH, H 2 SO 4 , KOH, etc. as electrolytes, which have problems when integrated with fuel cells and hybrids such as discomfort in movement and release of leakage. Therefore, such a supercapacitor in an aqueous solution is not capable of miniaturization as well as integration and simplification of processes in the electrolyte and electrode processes as described above.
다음 도 1은 통상의 코인형 전기 이중층 캐패시터(EDLC)의 구조를 나타낸 것으로, 활성탄 분말을 플루오린계 바인더와 혼합하여 시트상의 전극(5)을 제조하고, 상기 전극 시트를 원반형태로 펀칭(punching)하고 도전성 접착제(3)를 이용하여 캔(2) 및 케이스(11)에 접착하여 전극 및 단자를 완성한다. 이후, 양쪽 전극 사이에 분리막(4)을 삽입하고, 전해액을 함침한 후, 가스켓(7)을 삽입하여 상기 캔과 케이스를 봉합하여 코인형 셀을 제조한다. 1 shows a structure of a conventional coin-type electric double layer capacitor (EDLC), in which an activated carbon powder is mixed with a fluorine-based binder to prepare a sheet-
그러나, 종래의 코인형 EDLC는 액체 전해액을 사용함에 의해 치명적인 특성 저하 및 사용상의 한계가 발생된다. 대표적인 특성 저하로는 기판에 EDLC를 부착하는 리플로우(Reflow) 공정에서 솔더링 페이스트(Soldering paste)의 경화를 위해 260℃ 이상의 고온 분위기에서 상기EDLC를 노출하게 되는데 이때, 전해액의 기화에 의한 부피 팽창 및 내부압력 증가 현상이 발생되고 이로 인해 저항 증가 및 전해액의 누액이 발생되는 단점이 있다. However, the conventional coin type EDLC has a fatal property deterioration and limitation on use by using a liquid electrolyte. Representative degradation is to expose the EDLC in a high temperature atmosphere of 260 ℃ or more in order to cure the soldering paste (Soldering paste) in the reflow process of adhering the EDLC to the substrate, the volume expansion by the vaporization of the electrolyte and An increase in internal pressure occurs, which results in an increase in resistance and leakage of the electrolyte.
또한, 코인형 EDLC 의 경우 메모리 백업 전원으로서 휴대폰, 네비게이션 등의 전자 제품에 사용 되는데, 러시아, 북유럽, 등의 지역에서는 저온(-20℃이하)에서의 동작이 보증되어야 한다. In addition, the coin-type EDLC is used for electronic products such as mobile phones and navigation as a memory backup power supply. In Russia, Northern Europe, etc., operation at low temperature (below -20 ° C) should be guaranteed.
그러나, 액상 전해액의 경우 응고 현상이 발생되어 이온의 이동도(Mobility)가 저하되고 이로 인해, 저항이 급격히 증가하거나, 용량이 저하되는 등의 단점이 있어 사용상 많은 제약을 받고 있다. However, in the case of the liquid electrolyte solution, a solidification phenomenon occurs, and thus mobility of ions is lowered. As a result, there is a disadvantage in that the resistance is sharply increased or the capacity is decreased.
따라서, 상기의 문제점들을 극복하기 위해 다양한 시도들이 이뤄지고 있는 데, 예를 들면, 리플로우 공정에서의 전해액의 기화 현상을 방지하고, 저온 특성의 확보를 위해, 끓는점이 높은 폴리카보네이트(PC), 설포란(sulfolane SL), 이온성 액체 등의 용매를 사용한 전해액을 개발하고 있으나, 끓는점이 높은 용매의 경우, 점도가 높아 이온의 이동도(mobility)에 치명적인 악영향을 미치고, 이로 인해 100Ω 이상의 높은 저항을 보이는 단점을 가지고 있다.Therefore, various attempts have been made to overcome the above problems, for example, to prevent evaporation of the electrolyte in the reflow process and to secure low temperature properties, high boiling point polycarbonate (PC), Although electrolytes using solvents such as sulfolane SL and ionic liquids are being developed, high boiling point solvents have high viscosity and have a fatal adverse effect on the mobility of ions. It has a disadvantage.
따라서, 본 발명에서는 코인형 전기 이중층 캐패시터로 사용되는 액상 전해액 조성이 온도 변화에 따라 발생되는 여러가지 특성 저하로 인하여 캐패시터의 용량이 떨어지는 종래 기술에서의 문제들을 해결하고자 안출된 것이다.Therefore, in the present invention, the liquid electrolyte composition used as the coin-type electric double layer capacitor is designed to solve the problems in the prior art in which the capacity of the capacitor is lowered due to various deterioration caused by temperature change.
이에 본 발명에서는 종래 기술에서 전기 이중층 캐패시터의 특성 저하를 유발하는 액상의 전해액을 겔상의 이온 전도성 고분자 전해질로 대체하여 상기 문제점들을 해결할 수 있게 되었다. Therefore, in the present invention, it is possible to solve the above problems by replacing the liquid electrolyte that causes the deterioration of the characteristics of the electric double layer capacitor with a gel-like ion conductive polymer electrolyte.
따라서, 본 발명의 목적은 전기 이중층 캐패시터의 특성을 저하시키지 않는 겔상 전해액 조성물과 이의 제조방법을 제공하는 데 있다.Accordingly, it is an object of the present invention to provide a gel electrolyte composition and a method for producing the same which do not lower the characteristics of the electric double layer capacitor.
본 발명의 다른 목적은 상기 겔상 전해액 조성물로부터 제조된 겔 타입의 전해질층을 포함하는 전기 이중층 캐패시터를 제공하는 데도 있다. Another object of the present invention is to provide an electric double layer capacitor including a gel type electrolyte layer prepared from the gel electrolyte composition.
본 발명과 같이 겔상의 이온 전도성 고분자 전해질을 사용할 경우, 고온(260℃)에서 전해질의 상 변화가 발생하지 않아, 종래의 액상 전해액을 사용한 코인형 EDLC 셀의 저항 증가 및 용량 감소 등의 단점을 막을 수 있으며, 액상 전해액의 태생적인 불량인 누액 불량을 원천적으로 방지할 수 있다. 또한, 환경의 급격한 변화에서(-20℃~70℃)도 특성(용량 및 저항)의 편차가 심하지 않아 안정적인 특성 구현 을 할 수 있는 장점이 있다. 또한, 겔상의 이온 전도성 고분자 전해질층이 분리막 역할도 함께 할 수 있기 때문에 별도의 분리막을 사용하지 않아도 되며, 이로 인해 재료비 절감의 효과를 가진다. When using the gel-like ion conductive polymer electrolyte as in the present invention, the phase change of the electrolyte does not occur at a high temperature (260 ° C.), thereby preventing disadvantages such as increase in resistance and decrease in capacity of a coin-type EDLC cell using a conventional liquid electrolyte. In addition, it is possible to fundamentally prevent the leakage of leakage, which is a natural defect of the liquid electrolyte. In addition, there is an advantage that the characteristics (capacity and resistance) in the sudden change of the environment (-20 ℃ ~ 70 ℃) is not severe variation can be implemented a stable characteristic. In addition, since the gel-like ion conductive polymer electrolyte layer may also serve as a separator, it is not necessary to use a separate separator, thereby reducing the material cost.
상기와 같은 목적을 달성하기 위한 본 발명의 전기 이중층 캐패시터의 전해액 조성물은 전해질염 용액:이온 전도성 고분자 용액을 0.2:1 내지 1:1의 부피비로 혼합하여 이루어진 것을 그 특징으로 한다. The electrolyte solution composition of the electric double layer capacitor of the present invention for achieving the above object is characterized in that the electrolyte salt solution: ion-conducting polymer solution is made by mixing in a volume ratio of 0.2: 1 to 1: 1.
또한, 본 발명의 다른 목적을 달성하기 위한 전기 이중층 캐패시터의 전해액 조성물의 제조방법은 전해질염을 용매에 용해시켜 전해질염 용액을 제조하는 단계; 이온전도성 고분자를 용매에 용해시켜 이온전도성 고분자 용액을 제조하는 단계; 및 상기 전해질염 용액과 이온전도성 고분자 용액을 혼합하여 교반시키는 단계를 포함하는 것을 그 특징으로 한다.In addition, a method for preparing an electrolyte composition of an electric double layer capacitor for achieving another object of the present invention comprises the steps of dissolving an electrolyte salt in a solvent to prepare an electrolyte salt solution; Preparing an ion conductive polymer solution by dissolving the ion conductive polymer in a solvent; And a step of mixing and stirring the electrolyte salt solution and the ion conductive polymer solution.
또한, 본 발명의 추가의 다른 목적을 달성하기 위한 전기 이중층 캐패시터는 상기와 같은 전해액 조성물로부터 제조된 겔 타입의 전해질층을 포함하는 것을 그 특징으로 한다. In addition, an electric double layer capacitor for achieving another object of the present invention is characterized in that it comprises a gel-type electrolyte layer prepared from the electrolyte composition as described above.
이하 본 발명을 더욱 상세하게 설명하면 다음과 같다.Hereinafter, the present invention will be described in more detail.
본 발명은 전기 이중층 캐패시터에 사용되는 겔상 전해액 조성물과 이의 제보방법 및 이를 이용한 전기 이중층 캐패시터에 관한 것이다.The present invention relates to a gel electrolyte composition used in an electric double layer capacitor, a method for reporting the same, and an electric double layer capacitor using the same.
본 발명에 따른 전기 이중층 캐패시터용 겔상 전해액 조성물은 전해질염을 용매에 용해시켜 제조된 전해질염 용액과 이온 전도성 고분자를 용매에 용해시켜 제조된 이온 전도성 고분자 용액을 혼합하여 잘 교반시킴으로써 제조한다. The gel electrolyte composition for an electric double layer capacitor according to the present invention is prepared by mixing an electrolyte salt solution prepared by dissolving an electrolyte salt in a solvent and an ion conductive polymer solution prepared by dissolving an ion conductive polymer in a solvent and stirring well.
본 발명의 전해액 조성물에 포함되는 전해질염 용액은 암모늄 계열의 전해질염이나 리튬계 전해질염 중에서 선택된 1종 이상의 전해질염을 적절한 용매에 용해시켜 제조된 것이다.The electrolyte salt solution included in the electrolyte composition of the present invention is prepared by dissolving at least one electrolyte salt selected from an ammonium-based electrolyte salt or a lithium-based electrolyte salt in an appropriate solvent.
본 발명에 따른 상기 암모늄 계열의 전해질염으로는 테트라에틸 암모늄 테트라플루오로 보레이트(TEABF4), 테트라에틸메틸 암모늄 테트라플루오로보레이트(TEMABF4), 및 테트라에틸 암모늄 퍼클로로레이트(TEAClO4)로 이루어진 그룹으로부터 선택된 것이고, 리튬 계열의 전해질염은LiPF6, LiBF4, LiClO4, LiN(SO2CF3)2, LiN(SO2C2F5)2, LiC(SO2CF3)2, LiPF4(CF3)2, LiPF3(C2F5)3, LiPF3(CF3)3, LiPF5(iso-C3F7)3, LiPF5(iso-C3F7), (CF2)2(SO2)2NLi, 및 (CF2)3(SO2)2NLi로 이루어진 그룹으로부터 선택된 것이나, 이에 한정되지 않는다. The ammonium-based electrolyte salt according to the present invention comprises tetraethyl ammonium tetrafluoro borate (TEABF 4 ), tetraethylmethyl ammonium tetrafluoroborate (TEMABF 4 ), and tetraethyl ammonium perchlorate (TEAClO 4 ) Lithium-based electrolyte salt is selected from the group, LiPF 6 , LiBF 4 , LiClO 4 , LiN (SO 2 CF 3 ) 2 , LiN (SO 2 C 2 F 5 ) 2 , LiC (SO 2 CF 3 ) 2 , LiPF 4 (CF 3 ) 2 , LiPF 3 (C 2 F 5 ) 3 , LiPF 3 (CF 3 ) 3 , LiPF 5 (iso-C 3 F 7 ) 3 , LiPF 5 (iso-C 3 F 7 ), (CF 2 ) 2 (SO 2 ) 2 NLi, and (CF 2 ) 3 (SO 2 ) 2 NLi, but is not limited thereto.
또한, 상기 전해질염을 용해시키는 용매로는 에틸렌 카보네이트(EC), 프로필렌 카보네이트(PC), 부틸렌 카보네이트(BC), 및 비닐에틸렌 카보네이트(VEC)로 이루어진 그룹으로부터 선택된 환형 카보네이트; 디메틸 카보네이트(DMC), 메틸에틸 카보네이트(MEC), 디에틸 카보네이트(DEC), 메틸프로필 카보네이트(MPC), 디프로필 카보네이트(DPC), 메틸부틸 카보네이트(MBC), 및 디부틸 카보네이트(DBC)로 이루어진 그룹으로부터 선택된 선형 카보네이트; γ-부티로락톤(GBL), γ-발레롤락 톤(GVL), 및 α-안젤리카 락톤(AGL)으로 이루어진 그룹으로부터 선택된 락톤; 테트라히드로푸란, 2-메틸 테트라히드로푸란, 1,4-디옥산, 1,2-디메톡시 에탄, 1,2-디에톡시에탄 및 1,2-디부톡시에탄으로 이루어진 그룹으로부터 선택된 에테르; 아세토니트릴, 및 아디포니트릴과 같은 니트릴; 프로피온산메틸, 피발산 메틸, 피발산 부틸, 및 피발산 옥틸로 이루어진 그룹으로부터 선택된 선형 에스테르; 디메틸포름아미드와 같은 아미드; 인산트라이메틸 또는 인산트리옥틸과 같은 인산에스테르; 및 디메틸 술폰, 다이비닐설폰과 같은 S=O 기 함유 화합물로 이루어진 그룹으로부터 선택된 1종 이상의 것이나, 이에 한정되는 것은 아니다. In addition, the solvent for dissolving the electrolyte salt is a cyclic carbonate selected from the group consisting of ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), and vinyl ethylene carbonate (VEC); Consisting of dimethyl carbonate (DMC), methylethyl carbonate (MEC), diethyl carbonate (DEC), methylpropyl carbonate (MPC), dipropyl carbonate (DPC), methylbutyl carbonate (MBC), and dibutyl carbonate (DBC) Linear carbonates selected from the group; lactones selected from the group consisting of γ-butyrolactone (GBL), γ-valerolactone (GVL), and α-angelica lactone (AGL); Ethers selected from the group consisting of tetrahydrofuran, 2-methyl tetrahydrofuran, 1,4-dioxane, 1,2-dimethoxy ethane, 1,2-diethoxyethane and 1,2-dibutoxyethane; Nitriles such as acetonitrile, and adiponitrile; Linear esters selected from the group consisting of methyl propionate, methyl pivalate, butyl pivalate, and octyl pivalate; Amides such as dimethylformamide; Phosphate esters such as trimethyl phosphate or trioctyl phosphate; And S = O group-containing compounds such as dimethyl sulfone and divinyl sulfone, but are not limited thereto.
상기 전해질염 용액은 상기 전해질염을 0.2 내지 2M의 농도로 유지하는 것이 최적의 이온전도도 성능을 발휘하는 면에서 바람직하다며, 전해질염의 농도가 0.2M 미만이면 이온 전도도가 너무 낮아지고, 2.0M을 초과하게 되면 몰수가 증가하여도 이온전도도는 증가하지 않기 때문이다.The electrolyte salt solution is preferable to maintain the electrolyte salt at a concentration of 0.2 to 2M in terms of exhibiting the optimum ion conductivity performance, if the concentration of the electrolyte salt is less than 0.2M ionic conductivity is too low, exceeding 2.0M This is because the ion conductivity does not increase even if the number of moles increases.
또한, 본 발명의 전해액 조성에 포함되는 다른 성분으로는 이온전도성 고분자를 용매에 용해시켜 제조된 이온 전도성 고분자 용액이다. In addition, another component included in the electrolyte composition of the present invention is an ion conductive polymer solution prepared by dissolving an ion conductive polymer in a solvent.
상기 이온 전도성 고분자는 폴리에틸렌옥사이드(PEO), 폴리비닐리덴플로로-co-헥사플루오로 포스페이트(PVDF-co-HFP), 폴리메틸메타크릴레이트(PMMA), 폴리에틸렌디옥시티오펜(PEDOT), 폴리피롤(PPY), 폴리아크릴로니트릴(PAN), 폴리아닐린, 및 폴리아세틸렌으로 이루어진 그룹으로부터 선택된 1종 이상의 것이나, 상기 이온 전도성 고분자 이외에 전도성을 띄는 고분자라면 이에 한정되지 않는다. The ion conductive polymer is polyethylene oxide (PEO), polyvinylidene fluoro-co-hexafluoro phosphate (PVDF-co-HFP), polymethyl methacrylate (PMMA), polyethylene dioxythiophene (PEDOT), polypyrrole ( PPY), at least one selected from the group consisting of polyacrylonitrile (PAN), polyaniline, and polyacetylene, but is not limited thereto as long as the polymer exhibits conductivity in addition to the ion conductive polymer.
또한, 상기 이온 전도성 고분자를 용해시키는 용매로는 에틸렌 카보네이 트(EC), 디메틸포름알데히드(DMF), 디메틸클로라이드, 디에틸클로라이드, 아세톤, 벤젠, 클로로포름, 톨루엔, 및 N-메틸피롤리돈(NMP)로 이루어진 그룹으로부터 선택된 1종 이상의 것이나, 이에 한정되는 것은 아니다. In addition, as the solvent for dissolving the ion conductive polymer, ethylene carbonate (EC), dimethyl formaldehyde (DMF), dimethyl chloride, diethyl chloride, At least one selected from the group consisting of acetone, benzene, chloroform, toluene, and N-methylpyrrolidone (NMP), but is not limited thereto.
본 발명의 이온 전도성 고분자 용액은 필요에 따라 가교제를 더 포함할 수 있는데, 이는 전해질 조성의 기계적 강도를 높이기 위하여 포함되며, 구체적으로는 에틸렌글리콜, 폴리비닐리덴 풀루오라이드-헥사풀루오로프로필렌(polyvinylidenefluoride-co-hexafluoropropylene), 폴리비닐리덴 풀루오라이드-트리클로로에틸렌 (polyvinylidene fluoride-cotrichloroethylene), 폴리메틸메타크릴레이트 (polymethylmethacrylate), 폴리아크릴로니트릴(polyacrylonitrile), 폴리비닐피롤리돈 (polyvinylpyrrolidone), 폴리비닐아세테이트(polyvinylacetate), 에틸렌 비닐 아세테이트 공중합체(polyethylene-co-vinyl acetate), 폴리에틸렌옥사이드(polyethylene oxide), 셀룰로오스 아세테이트(cellulose acetate), 셀룰로오스 아세테이트 부틸레이트 (cellulose acetate butyrate), 셀룰로오스 아세테이트 프로피오네이트(cellulose acetate propionate), 시아노에틸풀루란 (cyanoethylpullulan), 시아노에틸폴리비닐알콜(cyanoethylpolyvinylalcohol), 시아노에틸셀룰로오스 (cyanoethylcellulose), 시아노에틸수크로오스(cyanoethylsucrose), 풀루란 (pullulan), 카르복실 메틸 셀룰로오스 (carboxyl methyl cellulose), 아크리로니트릴스티렌부타디엔 공중합체 (acrylonitrile-styrene-butadiene copolymer), 폴리이미드(polyimide) 및 이들의 혼합물로 이루어진 그룹으로부터 선택된 1종 이상이나 이에 한정되는 것은 아니다. The ion conductive polymer solution of the present invention may further comprise a crosslinking agent, if necessary, which is included to increase the mechanical strength of the electrolyte composition, specifically, ethylene glycol, polyvinylidene fluoride-hexafuluropropylene ( polyvinylidenefluoride-co-hexafluoropropylene, polyvinylidene fluoride-cotrichloroethylene, polymethylmethacrylate, polyacrylonitrile, polyvinylpyrrolidone, Polyvinylacetate, ethylene vinyl co-vinyl acetate, polyethylene oxide, cellulose acetate, cellulose acetate butyrate, cellulose acetate propionate (cellulose acetate propionate ), Cyanoethylpullulan, cyanoethylpolyvinylalcohol, cyanoethylcellulose, cyanoethylsucrose, pullulan, carboxyl methyl cellulose At least one selected from the group consisting of cellulose, acrylonitrile-styrene-butadiene copolymer, polyimide, and mixtures thereof, but is not limited thereto.
상기 이온 전도성 고분자 용액은 상기 이온 전도성 고분자를 1 내지 20중량%의 농도로 용해시키는 것이 고체 고분자 막의 안정적인 물리적 또는 화학적 특성 및 전기화학적 특성(이온 전도도 등)을 발휘하는 측면에서 바람직하다.In the ion conductive polymer solution, dissolving the ion conductive polymer at a concentration of 1 to 20% by weight is preferable in view of exhibiting stable physical or chemical properties and electrochemical properties (ion conductivity, etc.) of the solid polymer membrane.
또한, 본 발명에 따른 전기 이중층 캐패시터의 전해액 조성물은 상기 전해질염 용액:이온 전도성 고분자 용액을 0.2:1 내지 1:1의 부피비로 혼합하여 제조할 수 있는 바, 혼합 비율이 상기 범위를 벗어날 경우 전체 전해액 조성물 내에서 상기 전해질염이 고르게 분산되지 못하고 염(salt) 상태로 석출되는 문제가 있어 바람직하지 못하다.In addition, the electrolyte composition of the electric double layer capacitor according to the present invention can be prepared by mixing the electrolyte salt solution: ion conductive polymer solution in a volume ratio of 0.2: 1 to 1: 1, if the mixing ratio is out of the range, the whole It is not preferable because the electrolyte salt is not evenly dispersed in the electrolyte composition and precipitates in a salt state.
즉, 본 발명에 따른 전해액 조성물은 상기 전해질염 용액을 제조하고, 이와는 별도로 이온 전도성 고분자 용액을 제조한 다음, 이를 적절한 혼합 비율로 혼합하고, 충분하게 교반시킴으로써 제조할 수 있다.That is, the electrolyte composition according to the present invention may be prepared by preparing the electrolyte salt solution, separately preparing an ion conductive polymer solution, and then mixing them in an appropriate mixing ratio and sufficiently stirring the solution.
이는 전해질염이 용매에 용해되면 리튬과 암모늄이 이온 상태로 존재하게 되고, 또한 이온 전도성 고분자가 용매에 용해되면 상기 이온 전도성 고분자들이 단분자 형태로 용매 내에서 잘 분산되게 된다. 따라서, 이들 두 용액을 적절한 비율로 혼합하게 되면, 단분자 형태로 분산된 이온 전도성 고분자들 사이사이로 상기 리튬 이온과 암모늄 이온이 균일하게 분산된 형태로 존재하게 되고, 외부로부터 전기가 가해지면 상기 이온들의 이동도(mobility)가 좋아지게 되어, 저항이 증가되어 캐패시터의 용량이 감소되는 문제를 발생시키지 않는 효과를 가진다. When the electrolyte salt is dissolved in a solvent, lithium and ammonium are present in an ionic state, and when the ion conductive polymer is dissolved in a solvent, the ion conductive polymers are dispersed in the solvent in the form of a single molecule. Therefore, when these two solutions are mixed in an appropriate ratio, the lithium ions and ammonium ions are uniformly dispersed between the ion conductive polymers dispersed in the form of a single molecule, and when the ions are applied from outside, the ions Their mobility is improved, so that the resistance is increased so that the capacity of the capacitor is reduced.
그러나, 상기 전해질염과 이온 전도성 고분자를 1액형으로 하나의 용액으로 제조하게 되면 상기와 같은 구조로 용액 내에서 분산되지 않기 때문에 본 발명과 같은 효과를 얻을 수 없다. However, when the electrolyte salt and the ion conductive polymer are prepared in one solution in one solution, the same effect as the present invention cannot be obtained because the electrolyte salt and the ion conductive polymer are not dispersed in the solution as described above.
한편, 본 발명은 상기와 같은 특성을 가지는 전해질 조성물을 이용한 전기 이중층 캐패시터에도 특징이 있다.On the other hand, the present invention also features an electric double layer capacitor using the electrolyte composition having the above characteristics.
본 발명에 따른 전기 이중층 캐패시터는 다음 도 3과 같이 활성탄, 도전제, 및 바인더를 용매에 용해시켜 제조된 전극 슬러리로부터 양극과 음극의 전극을 제조하고, 이를 케이스 및/또는 캔과 접착시켜 건조시킨다. 그 다음, 상기와 같은 조성으로부터 제조된 겔 타입의 전해질을 도포시키고, 여기에 가스켓을 삽입한 후, 셀을 봉합시키면 코인 형태로 제조할 수 있게 된다.In the electric double layer capacitor according to the present invention, the electrode of the positive electrode and the negative electrode is prepared from an electrode slurry prepared by dissolving activated carbon, a conductive agent, and a binder in a solvent as shown in FIG. . Then, a gel-type electrolyte prepared from the composition described above is applied, a gasket is inserted therein, and the cell is sealed to prepare a coin.
또한, 본 발명의 전기 이중층 캐패시터의 전극에 사용되는 전극 활물질, 도전제, 바인더, 및 용매는 통상의 캐패시터에 사용되는 것이면 그 종류나 함량이 한정되지 않는다. In addition, the electrode active material, the conductive agent, the binder, and the solvent used for the electrode of the electric double layer capacitor of the present invention are not limited in kind and content as long as they are used in ordinary capacitors.
본 발명에 따라 제조된 겔 타입의 전해질을 포함하는 전기 이중층 캐패시터의 경우 다음 도 4에서와 같이, 상기 겔 타입의 전해질층(8)이 분리막의 역할도 함께 수행할 수 있기 때문에 별도의 분리막을 포함하지 않아도 되므로, 분리막 포함에 따른 비용절감이나 공정의 단순화를 꾀할 수 있는 추가의 효과를 가진다. 즉, 분리막과 전극과의 배열(align)이 맞지 않는 경우, 단락(Short)이 발생되는 치명적인 불량을 근본적으로 제거할 수 있는 장점이 있다. In the case of an electric double layer capacitor including a gel-type electrolyte prepared according to the present invention, as shown in FIG. 4, since the gel-
이하 본 발명을 실시예에 의거하여 더욱 상세하게 설명하면 다음과 같으나, 본 발명이 이에 한정되는 것은 아니다. Hereinafter, the present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.
실시예 1 Example 1
<겔 타입의 전해질 제조><Gel type electrolyte preparation>
다음 도 2와 같은 공정에 따라 전해질염 LiPF6 1.0 몰 농도를 제조하였다. 이와는 별도로, 이온 전도성 고분자로 폴리에틸렌옥사이드 6.0g 와 가교제로서 에틸렌글리콜 3.0g을 에틸렌 카보네이트(EC) 33.0g 에 용해시켜 이온전도성 고분자 용액을 제조하였다. Next, 1.0 mol of electrolyte salt LiPF 6 was prepared according to the process as shown in FIG. 2. Separately, 6.0 g of polyethylene oxide as an ion conductive polymer and 3.0 g of ethylene glycol as a crosslinking agent were dissolved in 33.0 g of ethylene carbonate (EC) to prepare an ion conductive polymer solution.
상기 전해질염 용액과 이온 전도성 고분자 용액을 부피비로 1:1 로 혼합하고 교반시켜 전기 이중층 캐패시터용 전해질 조성물을 제조하였으며, 이 조성물을 용액-캐스팅 방법(solution-casting method)으로 도포시켜 겔 타입의 전해질을 제조하였다. The electrolyte salt solution and the ion conductive polymer solution were mixed at a volume ratio of 1: 1 and stirred to prepare an electrolyte composition for an electric double layer capacitor, and the composition was applied by a solution-casting method to apply a gel type electrolyte. Was prepared.
<전극 제조>Electrode Fabrication
활성탄으로는 MSP, 도전제로는 Super P, 바인더 폴리테트라플루오로에틸렌(PTFE)를 용매 이소프로필알콜에 용해시켜 전극 슬러리를 제조하고, 이를 Kneading Method를 통하여 450um 두께의 전극을 제조하였다. MSP as activated carbon, Super P as a conductive agent, and binder polytetrafluoroethylene (PTFE) were dissolved in solvent isopropyl alcohol to prepare an electrode slurry, and a 450um thick electrode was prepared through the kneading method.
<코인 형태의 셀 제조>Coin Cell Production
다음 도 3과 같은 공정에 따라 상기 제조된 전극을 φ18 크기의 원형 형태로 펀칭하여 양극 및 음극을 제조하고, 이를 도전성 접착제를 이용하여 φ20 크기의 케이스와 캔에 접착하여 200℃의 온도에서 24시간 건조시켰다. 상기 제조된 겔 타입의 전해질을 상기 건조된 소자에 도포시켜 전해질층을 형성시킨 후, 가스켓을 삽입시켰다. 겔 타입의 전해질층이 도포된 소자들을 Crimper를 이용하여 밀봉하여 코인 형태의 셀을 제조하였다. Next, according to the process as shown in Figure 3 by punching the prepared electrode in a circular shape of φ18 size to produce a positive electrode and a negative electrode, using a conductive adhesive to adhere to the case and can of φ20 size 24 hours at a temperature of 200 ℃ Dried. The prepared gel-type electrolyte was applied to the dried device to form an electrolyte layer, and then a gasket was inserted. The cells in which the gel-type electrolyte layer was applied were sealed using a crimper to prepare a coin-shaped cell.
상기 제조된 셀의 전기화학적 특성을 다음과 같이 평가하였으며, 그 결과를 다음 표 1에 나타내었다.The electrochemical properties of the prepared cells were evaluated as follows, and the results are shown in Table 1 below.
-내부저항 : 충방전기를 이용하여 일정 전류(약 100mA)로 방전시키고, 초기 방전이 일어나는 10밀리초(ms) 동안 발생한 IR Drop 전압을 측정하여 V=IR 식에 대입하여 계산하였다. -Internal resistance: The battery was discharged at a constant current (about 100 mA) using a charger and a discharger, and the IR drop voltage generated for 10 milliseconds (ms) during the initial discharge was measured and substituted by V = IR.
-고온 부하 용량 변화율 : 70℃에서 정격 전압(3.3V)를 인가하면서 일정시간(100시간 간격) 간격으로 테스트 셀의 정전용량을 측정한고, 측정된 정전 용량을 상온에서 측정된 정전용량과 비교하여 용량 변화율을 계산하였다. -High temperature load capacity change rate: Measure the capacitance of the test cell at regular intervals (100 hours interval) while applying the rated voltage (3.3V) at 70 ℃, and compare the measured capacitance with the capacitance measured at room temperature Dose rate of change was calculated.
-고온 부하 완료 후 내부 저항 : 고온 부하 테스트를 진행한 후, 상기 기록한 내부 저항 측정법을 활용하여 상온에서 테스트하고 결과를 식에 대입하여 계산하였다. Internal resistance after completion of high temperature load: After carrying out the high temperature load test, the test was performed at room temperature using the internal resistance measurement method described above and calculated by substituting the result into the equation.
-저온 방전 용량 변화율 : -20℃에서 정격 전압(3.3V)를 인가하면서 일정시간(100시간 간격) 간격으로 테스트 셀의 정전용량을 측정하고, 측정된 정전 용량을 상온에서 측정된 정전용량과 비교하여 용량 변화율을 계산하였다.-Low temperature discharge capacity change rate: Measure the capacitance of the test cell at regular intervals (100 hours interval) while applying rated voltage (3.3V) at -20 ℃, and compare the measured capacitance with the capacitance measured at room temperature. Dose change rate was calculated.
-고온 방전 용량 변화율 : 70℃에서 방전을 실시한 후, 정전용량을 측정하고, 측정된 정전 용량을 상온에서 측정된 정전용량과 비교하여 용량 변화율을 계산 하였다.-High temperature discharge capacity change rate: After discharge at 70 ℃, the capacitance was measured, the capacity change rate was calculated by comparing the measured capacitance with the capacitance measured at room temperature.
-충방전 용량 변화율 : 0V에서 3.3V 까지 일정 전류(약 10mA)로 충전과 방전을 실시한 것을 1cycle이라 하며, 이를 상온에서 10,000cycle 실시한다. 그리고 일정 간격으로 테스트 셀의 정전용량을 측정하여 cycle 전 정전용량과 비교하였다. -Charge / discharge capacity change rate: Charge and discharge with a constant current (about 10mA) from 0V to 3.3V is called 1cycle, which is 10,000cycle at room temperature. And the capacitance of the test cell was measured at regular intervals and compared with the capacitance before cycle.
상기 표 1의 결과에서 확인할 수 있는 바와 같이, 휴대폰 RTC Back-up 용 캐패시터의 요구 기준(spec)에 비하여 초기 용량과 내부 저항이 우수하고 고온 부하 및 저온/고온 방전, 그리고 충방전 특성이 상기 기준에 만족함을 확인할 수 있었다. As can be seen from the results of Table 1, the initial capacity and internal resistance is excellent and the high temperature load, low temperature / high temperature discharge, and charge / discharge characteristics are higher than the required specifications of the capacitor for the mobile phone RTC back-up. Satisfaction with was confirmed.
본 발명의 실시예에 따라 본 발명을 설명하였으나 본 발명이 속하는 기술 분야에서 통상의 지식을 가진 자가 본 발명의 기술적 사상을 벗어나지 않는 범위 내에서 변경 및 변형한 것도 포함된다.Although the present invention has been described in accordance with embodiments of the present invention, modifications and variations may be made by those skilled in the art without departing from the technical spirit of the present invention.
도 1은 통상의 전기 이중층 캐패시터의 구조이고,1 is a structure of a conventional electric double layer capacitor,
도 2는 본 발명에 따른 겔 타입 전해질을 제조하는 과정을 나타낸 공정도이고,2 is a process chart showing a process for preparing a gel type electrolyte according to the present invention,
도 3은 본 발명에 따른 겔 타입 전해질을 포함하는 전기 이중층 캐패시터의 제조 공정도이고,3 is a manufacturing process chart of an electric double layer capacitor including a gel type electrolyte according to the present invention,
도 4는 본 발명에 따른 겔 타입 전해질층을 포함하는 전기 이중층 캐패시터의 구조이다.4 is a structure of an electric double layer capacitor including a gel type electrolyte layer according to the present invention.
<도면 부호의 설명>≪ Description of reference numerals &
2 : 상부 Can 2: Upper Can
3 : 도전성 접착제3: conductive adhesive
4 : 분리막4: separator
5 : 활성탄 전극 5: activated carbon electrode
7 : Gasket7: Gasket
8 : 겔 타입 전해질층8: gel type electrolyte layer
11 : 하부 Case11: Lower Case
Claims (12)
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| KR1020080095241A KR101531955B1 (en) | 2008-09-29 | 2008-09-29 | Gel-type electrolyte composition for electric double layer capacitors, method of preparing the same, and electric double layer capacitors comprising electrolyte layer |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011154766A1 (en) * | 2010-06-08 | 2011-12-15 | Indian Institute Of Technology Bombay | Pan-peo gels with improved conductance and solvent retention |
| US8673503B2 (en) | 2010-06-04 | 2014-03-18 | Indian Institute Of Technology Bombay | Polyurethane gel electrolytes with improved conductance and/or solvent retention |
| CN104867692A (en) * | 2015-04-03 | 2015-08-26 | 安徽江威精密制造有限公司 | Copper-tin-alloy-coated straw based active carbon electrode material and preparation method thereof |
| KR101583525B1 (en) * | 2014-10-31 | 2016-01-11 | 주식회사 알파켐 | electrolytic solution for supercapacitor and supercapacitor use the same |
| CN110590995A (en) * | 2019-09-19 | 2019-12-20 | 西安交通大学 | Preparation method of phase-change gel |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100273506B1 (en) * | 1997-11-14 | 2000-12-15 | 유현식 | Polymer gel and manufacturing method for secondary battery |
| KR100353867B1 (en) * | 1999-11-30 | 2002-09-26 | 한국전자통신연구원 | Polymer Electrolyte for Rechargeable Lithium Batteries |
| JP4517440B2 (en) * | 2000-03-10 | 2010-08-04 | ソニー株式会社 | Lithium ion solid electrolyte secondary battery |
| KR100533647B1 (en) * | 2002-09-30 | 2005-12-06 | 한국과학기술연구원 | A uv-cured multi-component polymer blend electrolyte, lithium secondary battery and their fabrication method |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8673503B2 (en) | 2010-06-04 | 2014-03-18 | Indian Institute Of Technology Bombay | Polyurethane gel electrolytes with improved conductance and/or solvent retention |
| WO2011154766A1 (en) * | 2010-06-08 | 2011-12-15 | Indian Institute Of Technology Bombay | Pan-peo gels with improved conductance and solvent retention |
| US8871390B2 (en) | 2010-06-08 | 2014-10-28 | Indian Institute Of Technology Bombay | PAN-PEO gels with improved conductance and solvent retention |
| KR101583525B1 (en) * | 2014-10-31 | 2016-01-11 | 주식회사 알파켐 | electrolytic solution for supercapacitor and supercapacitor use the same |
| CN104867692A (en) * | 2015-04-03 | 2015-08-26 | 安徽江威精密制造有限公司 | Copper-tin-alloy-coated straw based active carbon electrode material and preparation method thereof |
| CN110590995A (en) * | 2019-09-19 | 2019-12-20 | 西安交通大学 | Preparation method of phase-change gel |
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| KR101531955B1 (en) | 2015-06-26 |
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