WO2013147435A1 - Electrolyte having enhanced high-rate charge/discharge properties and capacitor comprising same - Google Patents

Electrolyte having enhanced high-rate charge/discharge properties and capacitor comprising same Download PDF

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Publication number
WO2013147435A1
WO2013147435A1 PCT/KR2013/001919 KR2013001919W WO2013147435A1 WO 2013147435 A1 WO2013147435 A1 WO 2013147435A1 KR 2013001919 W KR2013001919 W KR 2013001919W WO 2013147435 A1 WO2013147435 A1 WO 2013147435A1
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electrolyte
formula
group
capacitor
discharge characteristics
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PCT/KR2013/001919
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French (fr)
Korean (ko)
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정철수
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서울시립대학교 산학협력단
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Publication of WO2013147435A1 publication Critical patent/WO2013147435A1/en
Priority to US14/501,927 priority Critical patent/US20150024267A1/en

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    • 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
    • H01G11/64—Liquid electrolytes characterised by additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/022—Electrolytes; Absorbents
    • H01G9/035—Liquid electrolytes, e.g. impregnating materials
    • 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
    • H01G11/04—Hybrid capacitors
    • H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
    • 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
    • H01G11/60—Liquid electrolytes characterised by the solvent
    • 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
    • H01G11/62—Liquid electrolytes characterised by the solute, e.g. salts, anions or cations therein

Definitions

  • the present invention relates to an electrolyte for a capacitor having a high rate charging and discharging characteristic and a capacitor including the same, and more particularly, to prevent unnecessary overvoltage during charging and discharging of an electrochemical capacitor such as a supercapacitor, a lithium ion capacitor, and the like. It relates to an electrolyte for a capacitor and a capacitor including the same that can be improved.
  • electrochemical energy storage devices are a key component of finished devices essential for all portable information and communication devices and electronic devices.
  • electrochemical energy storage devices will be reliably used as high quality energy sources in the renewable energy field that can be applied to future electric vehicles and portable electronic devices.
  • the electrochemical capacitors of the electrochemical energy storage device may be classified into an electric double layer using an electric double layer principle and a hybrid supercapacitor using an electrochemical conversion-reduction reaction.
  • the electric double layer capacitor is used in many fields that require high output energy characteristics, but the electric double layer capacitor has a disadvantage of being used for a small capacity.
  • hybrid supercapacitors are being researched as a new alternative to improve the capacity characteristics of electric double layer capacitors.
  • the lithium ion capacitor of the hybrid supercapacitor may have an accumulation capacity of about 3 to 4 times that of the electric double layer capacitor.
  • the electrolytes used in high capacity capacitors are classified into aqueous electrolytes, non-aqueous electrolytes and solid electrolytes.
  • the aqueous electrolyte has a high conductivity to reduce the internal resistance of the basic cell, but the energy density of the capacitor is low due to the low operating voltage.
  • non-aqueous electrolytes generally have a higher viscosity than aqueous electrolytes and have a conductivity of about 1/10 to 1/100 times lower. Therefore, when the non-aqueous electrolyte is used, the output resistance is worse than that of the aqueous electrolyte due to the increased internal resistance.
  • the potential difference is high, and the energy density of the capacitor which is proportional to the square of the voltage used can be greatly increased, the usable temperature range is wide, and the high pressure resistance and miniaturization can be achieved. Research is actively underway.
  • Lithium-ion capacitors are oxidized as a feature of the capacitor electrode in the positive electrode (active carbon) during charging, and the negative ions in the electrolyte are adsorbed on the positive electrode to maintain a stable voltage.
  • the negative electrode graphite acts as a stable negative electrode by inserting lithium ions as in the negative electrode of the lithium secondary battery.
  • the electrolytic salt dissolved in the electrolyte plays a role of stably maintaining the charging voltage of the lithium ion capacitor without generating an overvoltage.
  • an object of the present invention is to provide an electrolyte for a capacitor and a capacitor including the same, which can improve the high-rate charging and discharging characteristics of the capacitor by preventing unnecessary overvoltage during charging and discharging such as an electrochemical capacitor and a lithium ion capacitor. have.
  • the present invention is an aromatic compound included in at least one of the following Chemical Formulas 1 to 11 that can induce a resonance effect of electron transfer, the functional group is present at a position that can structurally suppress local polarization phenomenon
  • An organic compound having a boiling point of 80 ° C. or more includes a substituent, and in Formulas 1 to 11, R is an electrolyte having improved high-rate charging and discharging characteristics, wherein at least one functional group is selected from alkyl groups of methyl, ethyl, propyl, and butyl. .
  • R is located at 1,3, n is 2.
  • R is located at 1,4 or 1,3,5, n is 2,3.
  • R is located at 1,5 or 1,3,5,7, n is 2,4.
  • R is 1,6 position, 1,3,5,7 position, 1,2,7,8 position, 1,3,5,7,9 position, 1,2,3,6,7,8 position and 1 Located at any of 2,3,4,6,7,8,9 positions.
  • n is 2,4,5,6,8.
  • R is 1,6 position, 1,3,5,7 position, 1,2,7,8 position, 1,3,5,7,9 position, 1,2,3,6,7,8 position and 1 Located at any of 2,3,4,6,7,8,9 positions.
  • n is 2,4,5,6,8.
  • R is located at any one of 2,4 position, 3,5 position, 3,4 position and 2,5 position.
  • n is 2.
  • R is located at any one of 2,4 position, 3,5 position, 3,4 position and 2,5 position.
  • n is 2.
  • R is located at any one of 2,4 position, 3,5 position, 3,4 position and 2,5 position.
  • n is 2.
  • R is located at 2,4,6, n is 3.
  • R is located at 2,5, n is 2.
  • R is located at 2,4,6 or 2,4,5,7 and n is 3,4.
  • R is a functional group of any one of alkoxy groups of methoxy, ethoxy, propanoxy and butoxy. It provides an electrolyte with improved high rate charge and discharge characteristics.
  • the present invention provides an electrolyte with improved high-rate charging and discharging characteristics, characterized in that R is any one functional group among fluoro, chloro and bromo.
  • the present invention is that the alkyl group in Formula 1 to Formula 11 that any one of the acetyl group, aldehyde group, amine group, amine group, ester group, ether group Provided is an electrolyte having improved high rate charge / discharge characteristics.
  • the present invention is a high-yield characterized in that the hydrogen (H) connected to the carbon (C) structurally connected to the alkyl group is substituted with any one of fluoro (chloro), chloro (bro) and bromo (bromo) It provides an electrolyte with improved discharge characteristics.
  • the present invention provides an electrolyte with improved high rate charge and discharge characteristics, characterized in that the aromatic compound comprises 1 to 10 parts by weight based on 100 parts by weight of the electrolyte.
  • the present invention provides an electrolyte with improved high rate charge and discharge characteristics, the electrolyte comprising the aromatic compound, an electrolytic salt and a non-aqueous organic solvent.
  • the electrolytic salt is LiPF 6 , LiBF 4 , LiTFSI, LiSbF 6 , LiAsF 6 , LiClO 4 , LiCF 3 SO 3 , Li (CF 3 SO 2 ) 2 N, LiC 4 F 9 SO 3 , LiSbF 6 , LiAlO 4 , LiAlCl 4 , LiN (C x F 2x + 1 SO 2 ) (C y F 2y + 1 SO 2 ) (where x, y is a natural number), LiCl, LiI, characterized in that at least one mixture in the group consisting of Provided is an electrolyte with improved high rate charge / discharge characteristics.
  • the non-aqueous organic solvent is ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), 1,2 -Dimethoxyethene (DME), ⁇ -butyrolactone (BL), tetrahydrofuran (THF), 1,3-dioxolane (DOL), diethylether (DEE), methyl formate (MF)
  • EC ethylene carbonate
  • PC propylene carbonate
  • DMC dimethyl carbonate
  • DEC diethyl carbonate
  • EMC ethyl methyl carbonate
  • EMC 1,2 -Dimethoxyethene
  • DME 1,3-dioxolane
  • DEE diethylether
  • MF methyl formate
  • the present invention provides a capacitor comprising the electrolyte.
  • the capacitor is manufactured using the electrolyte according to the present invention, even when an anion having a large electron density is used as the electrolyte salt, there is an effect of suppressing the strong adsorption of the anion with the electrode.
  • the capacitor according to the present invention has an effect of improving the high rate charge and discharge characteristics of the capacitor by preventing unnecessary overvoltage even during high rate charge and discharge.
  • the present inventors have developed an organic solvent having a relatively low polarity that can prevent the capacity decrease from occurring under electrolyte conditions using an anion having a high electron density, and when added to an electrolyte of an electrochemical capacitor such as a lithium ion capacitor, a high capacity even at a high rate
  • the present invention has been completed based on the fact that the capacitor can be implemented.
  • the present invention is characterized in that the electrolyte containing an aromatic compound included in at least one of the formulas (1) to (11).
  • R is located at 1,3, n is 2.
  • R is located at 1,4 or 1,3,5, n is 2,3.
  • R is located at 1,5 or 1,3,5,7, n is 2,4.
  • R is 1,6 position, 1,3,5,7 position, 1,2,7,8 position, 1,3,5,7,9 position, 1,2,3,6,7,8 position and 1 Located at any of 2,3,4,6,7,8,9 positions.
  • n is 2,4,5,6,8.
  • R is 1,6 position, 1,3,5,7 position, 1,2,7,8 position, 1,3,5,7,9 position, 1,2,3,6,7,8 position and 1 Located at any of 2,3,4,6,7,8,9 positions.
  • n is 2,4,5,6,8.
  • R is located at any one of 2,4 position, 3,5 position, 3,4 position and 2,5 position.
  • n is 2.
  • R is located at any one of 2,4 position, 3,5 position, 3,4 position and 2,5 position.
  • n is 2.
  • R is located at any one of 2,4 position, 3,5 position, 3,4 position and 2,5 position.
  • n is 2.
  • R is located at 2,4,6, n is 3.
  • R is located at 2,5, n is 2.
  • R is located at 2,4,6 or 2,4,5,7 and n is 3,4.
  • Formula 1 to Formula 11 includes an organic compound having a functional group at a position capable of structurally suppressing local polarization and having a boiling point of 80 ° C. or more, wherein the compound including Formula 1 to Formula 11 may Resonance effect can be induced.
  • Aromatic compounds in which functional groups such as electron donor groups or electron withdrawing groups exist in a position where structural polarization can be suppressed locally are polarized locally, but the polarization characteristics of the compound as a whole are lost. Since the cation can be suppressed from being strongly adsorbed, it is possible to create electrolyte conditions with excellent high rate charge / discharge characteristics.
  • the boiling point is to use an organic compound of less than 80 °C, it is not preferable because the high temperature characteristics of the capacitor deteriorate.
  • R may be one or more functional groups selected from alkyl groups of methyl, ethyl, propyl and butyl.
  • R may be any one of alkoxy groups of methoxy, ethoxy, propanoxy and butoxy.
  • R may be any one functional group among fluoro, chloro, and bromo.
  • the functional group including any one of an acetyl group, an aldehyde group, an amine group, an ester group, and an ether group in the alkyl group in Formulas 1 to 11 Can be.
  • R is one or more functional groups selected from alkyl groups of methyl, ethyl, propyl and butyl, and hydrogen (H) connected to carbon (C) structurally linked with the alkyl group is fluoro ( It may be substituted by any one of fluoro, chloro and bromo.
  • An electrolyte containing an aromatic compound made of any one of Formulas 1 to 11 may prevent a large electron density anion from being strongly adsorbed with an electrode, thereby realizing a capacitor having a high capacity even at a high rate.
  • the aromatic compound preferably contains 1 to 10 parts by weight based on 100 parts by weight of the electrolyte.
  • the electrolyte according to the present invention can be utilized in electrochemical capacitors such as supercapacitors, lithium ion capacitors, and the like, when the capacitor is prepared, the at least one compound selected from Chemical Formulas 1 to 11, electrolytic salts and non-aqueous systems It may consist of an organic solvent.
  • the electrolytic salts that may be used in the production of lithium ion capacitors include LiPF 6 , LiBF 4 , LiTFSI, LiSbF 6 , LiAsF 6 , LiClO 4 , LiCF 3 SO 3 , Li (CF 3 SO 2 ) 2 N, LiC 4 F 9 SO 3 , LiSbF 6 , LiAlO 4 , LiAlCl 4 , LiN (C x F 2x + 1 SO 2 ) (C y F 2y + 1 SO 2 ) (where x and y are natural numbers), LiCl, LiI, etc. It can be used as an electrolyte for lithium ion capacitors by mixing at least one group.
  • the non-aqueous organic solvent is ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC), ethylmethyl carbonate (EMC), 1,2-dimethoxy Ethene (DME), ⁇ -butyrolactone (BL), tetrahydrofuran (THF), 1,3-dioxolane (DOL), diethylether (DEE), methyl formate (MF), methylpro Pioneate (MP), sulfolane (S), dimethyl sulfoxide (DMSO) and acetonitrile (AN), etc. can be used as an electrolyte by mixing at least one.
  • EC ethylene carbonate
  • PC propylene carbonate
  • DMC dimethyl carbonate
  • DEC diethyl carbonate
  • EMC 1,2-dimethoxy Ethene
  • DME 1,3-dioxolane
  • DEE diethylether
  • MF methyl formate
  • the capacitor is manufactured using the electrolyte as described above, even if an anion having a large electron density is used as the electrolyte salt, there is an effect of suppressing the strong adsorption of the anion with the electrode. Therefore, overvoltage is not applied even at high rate charging and discharging, so that a capacitor having a high capacity can be realized.
  • the capacitor according to the present invention provides a capacitor including the positive electrode, the negative electrode, the separator and the electrolyte described above.
  • the electrode mixture of the positive electrode includes a positive electrode active material, a conductive material and a binder
  • the electrode mixture of the negative electrode includes a negative electrode active material, a conductive material and a binder
  • the cathode active material may be any carbon material having a double layer capacity, and may be used in the group consisting of activated carbon, natural fiber, amorphous carbon, fullerene, nanotube, graphene, and the like. Although it is not limited to the kind, it is preferable to use activated carbon with a large specific surface area and cheap.
  • any carbon material capable of adsorption and desorption with lithium ions may be used, and for example, natural graphite, artificial graphite, mixed mesocarbon, mixed carbon fiber, cocos, carbon material heat treated, etc. , Hard carbon, soft carbon and the like can be used.
  • the conductive material graphite, carbon black, acetylene black, Ketjen black, or the like can be used.
  • binder polyethylene, polypropylene, polyethylene terephthalate, aromatic polyamide, cellulose, styrene-butadiene rubber, or the like may be used, and the material is not particularly limited as long as it is a stable material for electrolyte.
  • the separator is located between the positive electrode and the negative electrode to prevent a short circuit caused by the contact between the two electrode plate active material and to hold and maintain the electrolyte solution required for the battery reaction.
  • the separator is not particularly limited as long as it is insulating and can penetrate the nonaqueous electrolyte. Specific examples thereof include polyethylene, vinylon, polyamide, polypropylene, polyvinyl chloride, polyethylene, and other porous materials having pores or pores.
  • the preparation of the electrolyte is an organic solvent in which ethylene carbonate (EC): diethyl carbonate (DEC) is mixed in a volume ratio of 30:70 and benzene of the formula (2) in 0.5M LiBF 4 , where n is 2, and 1,4-position
  • An electrolyte was prepared by mixing aromatic compounds in which fluoro was formed. The aromatic compound was added in 1 part by weight based on 100 parts by weight of the electrolyte.
  • Capacitors were manufactured by conventional methods known in the art, in which activated carbon and lithium metal were cut to a suitable size, and a separator made of a porous polyethylene film was inserted therebetween to prepare an electrode assembly. After inserting the electrode assembly into the pouch, the portion except the electrolyte injection hole was fused, and the prepared electrolyte was injected into the injection hole to complete the capacitor.
  • Example 2 the aromatic compound was added in 5 parts by weight (Example 2) and 10 parts by weight (Example 3) based on 100 parts by weight of the electrolyte.
  • the aromatic compound is benzene represented by Chemical Formula 2, n is 2, and an electrolyte is prepared by mixing an aromatic compound in which an ethyl group is formed at 1,4 positions. The aromatic compound was added in 1 part by weight based on 100 parts by weight of the electrolyte.
  • Example 5 the aromatic compound was added in 5 parts by weight (Example 5) and 10 parts by weight (Example 6) based on 100 parts by weight of the electrolyte.
  • the aromatic compound is pyrrole (Formula 6), n is composed of 2, an electrolyte was prepared by mixing an aromatic compound having a methoxy group formed at 2,4 positions. The aromatic compound was added in 1 part by weight based on 100 parts by weight of the electrolyte.
  • Example 8 the aromatic compound was added in 5 parts by weight (Example 8) and 10 parts by weight (Example 9) based on 100 parts by weight of the electrolyte.
  • the aromatic compound is pyrrole (Formula 6), n is composed of 2, an electrolyte was prepared by mixing an aromatic compound having a methoxy group formed at 2,4 positions. The aromatic compound was added in 1 part by weight based on 100 parts by weight of the electrolyte.
  • Example 11 the aromatic compound was added 5 parts by weight (Example 11) and 10 parts by weight (Example 12) based on 100 parts by weight of the electrolyte.
  • the aromatic compound is a furan (furan) of the general formula (7), n is composed of 2, an electrolyte was prepared by mixing an aromatic compound in which fluoro (fluoro) is formed in 2,4 positions. The aromatic compound was added in 1 part by weight based on 100 parts by weight of the electrolyte.
  • Example 14 the aromatic compound was added in 5 parts by weight (Example 14) and 10 parts by weight (Example 15) based on 100 parts by weight of the electrolyte.
  • the aromatic compound is cyclopentadiene represented by Chemical Formula 10, n is 2, and an electrolyte is prepared by mixing an aromatic compound in which an ethyl group is formed at 2,5 positions.
  • the aromatic compound was added in 1 part by weight based on 100 parts by weight of the electrolyte.
  • Example 17 the aromatic compound was added in 5 parts by weight (Example 17) and 10 parts by weight (Example 18) based on 100 parts by weight of the electrolyte.
  • an electrolyte was prepared by mixing an organic solvent and 0.5 M LiBF 4 mixed with ethylene carbonate (EC): diethyl carbonate (DEC) in a volume ratio of 30:70.
  • EC ethylene carbonate
  • DEC diethyl carbonate
  • Discharge capacities were measured after charging 0.2C, 1C, 2C, 5C, and 10C using the capacitors prepared in Examples and Comparative Examples. The measured results are shown in Table 1 below.

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  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
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Abstract

The present invention relates to an electrolyte having enhanced high-rate charge/discharge properties and a capacitor comprising same, and more specifically, to an electrolyte having enhanced high-rate charge/discharge properties and a capacitor comprising same, the electrolyte comprising an aromatic compound, which includes at least one of chemical formulas 1 to 11 that can induce electron spin resonance, and which is an organic compound of a substituent in which a functional group is present at a location that can structurally prevent local electrical polarization, and the boiling point of which is 80℃, wherein R in the chemical formulas 1 to 11 is at least one functional group selected from an alkyl group of methyl, ethyl, propyl, and butyl.

Description

고율충방전 특성이 향상된 전해질 및 이를 포함하는 캐패시터Electrolyte with improved high rate charge / discharge characteristics and capacitor including same
본 발명은 고율충방전 특성이 향상된 캐피시터용 전해질 및 이를 포함한 캐패시터에 관한 것으로 보다 상세하게는 슈퍼캐패시터, 리튬이온 캐패시터 등과 같은 전기화학 캐패시터의 충방전시 불필요한 과전압을 방지하여 캐패시터의 고율충방전 특성을 향상시킬 수 있는 캐패시터용 전해질 및 이를 포함한 캐패시터에 관한 것이다.The present invention relates to an electrolyte for a capacitor having a high rate charging and discharging characteristic and a capacitor including the same, and more particularly, to prevent unnecessary overvoltage during charging and discharging of an electrochemical capacitor such as a supercapacitor, a lithium ion capacitor, and the like. It relates to an electrolyte for a capacitor and a capacitor including the same that can be improved.
일반적으로, 전기화학적 에너지 저장장치는 모든 휴대용 정보통신기기, 전자기기에 필수적으로 사용되는 완제품 기기의 핵심부품이다. 또한, 전기화학적 에너지 저장장치는 미래형 전기자동차 및 휴대용 전자장치등에 적용될 수 있는 신재생 에너지 분야의 고품질 에너지원으로써 확실하게 사용될 것이다.In general, electrochemical energy storage devices are a key component of finished devices essential for all portable information and communication devices and electronic devices. In addition, electrochemical energy storage devices will be reliably used as high quality energy sources in the renewable energy field that can be applied to future electric vehicles and portable electronic devices.
전기화학적 에너지 저장장치 중 전기화학 캐패시터는 전기이중층 원리를 이용하는 전기이중층 캐패시터 (Electrical double layer)와 전기화학적 산환-환원 반응을 이용하는 하이브리드 슈퍼 캐패시터(Hybrid supercapacitor)로 구분될 수 있다.The electrochemical capacitors of the electrochemical energy storage device may be classified into an electric double layer using an electric double layer principle and a hybrid supercapacitor using an electrochemical conversion-reduction reaction.
여기서, 전기이중층 캐패시터는 고출력 에너지 특성을 필요로 하는 분야에서 많이 사용되고 있으나, 전기이중층 캐패시터는 작은 용량에 사용되는 단점을 가지고 있다. 이에 비해 하이브리드 슈퍼 캐패시터는 전기이중층 캐패시터의 용량 특성을 개선할 새로운 대안으로 많은 연구가 이루어지고 있다. 특히, 하이브리드 슈퍼 캐패시터 중 리튬이온 캐패시터는 전기이중층 캐패시터에 비해 3 내지 4배 정도의 축적용량을 가질 수 있다.Here, the electric double layer capacitor is used in many fields that require high output energy characteristics, but the electric double layer capacitor has a disadvantage of being used for a small capacity. In comparison, hybrid supercapacitors are being researched as a new alternative to improve the capacity characteristics of electric double layer capacitors. In particular, the lithium ion capacitor of the hybrid supercapacitor may have an accumulation capacity of about 3 to 4 times that of the electric double layer capacitor.
고용량 캐패시터에서 사용되는 전해질은 수계 전해질, 비수계 전해질 및 고체 전해질로 분류가 된다. 이 중 수계 전해질은 전도도가 커 기본 셀의 내부저항을 줄일 수 있으나 사용전압이 낮아 캐패시터의 에너지 밀도가 낮다.The electrolytes used in high capacity capacitors are classified into aqueous electrolytes, non-aqueous electrolytes and solid electrolytes. Among them, the aqueous electrolyte has a high conductivity to reduce the internal resistance of the basic cell, but the energy density of the capacitor is low due to the low operating voltage.
한편 비수계 전해질은 일반적으로 수계 전해질 보다 점도가 높고, 1/10~ 1/100 배 정도 낮은 전도도를 갖는다. 따라서 비수계 전해질을 사용하는 경우 내부저항이 커져서 출력 특성이 수계 전해질보다 좋지 못한 단점이 있다. 그러나 비수계 전해질의 경우, 적용 가능한 전위차가 높아 사용전압의 제곱에 비례하는 캐패시터의 에너지 밀도를 크게 높일 수 있고 사용가능한 온도 범위가 넓으며, 고내압화, 소형화 등이 가능하다는 장점이 있어 최근 이에 대한 연구가 활발히 진행되고 있다.On the other hand, non-aqueous electrolytes generally have a higher viscosity than aqueous electrolytes and have a conductivity of about 1/10 to 1/100 times lower. Therefore, when the non-aqueous electrolyte is used, the output resistance is worse than that of the aqueous electrolyte due to the increased internal resistance. However, in the case of the non-aqueous electrolyte, the potential difference is high, and the energy density of the capacitor which is proportional to the square of the voltage used can be greatly increased, the usable temperature range is wide, and the high pressure resistance and miniaturization can be achieved. Research is actively underway.
리튬이온 캐패시터의 경우 충전시에 양극(활성탄)에서 캐패시터 전극의 특징으로 산화되며, 이때 전해질에 있는 음이온이 양극에 흡착되어 안정한 전압을 유지하게 된다. 한편 충전시 음극(graphite)에서는 리튬이차전지의 음극에서와 같이 리튬이온이 삽입되어 안정된 음극으로서 작용하게 된다. 이때 리튬이온 캐패시터의 충전전압을 과전압 발생없이 안정적으로 유지시켜 주는 역할을 하는 것이 전해질에 녹아 있는 전해염이다.Lithium-ion capacitors are oxidized as a feature of the capacitor electrode in the positive electrode (active carbon) during charging, and the negative ions in the electrolyte are adsorbed on the positive electrode to maintain a stable voltage. On the other hand, when charging, the negative electrode (graphite) acts as a stable negative electrode by inserting lithium ions as in the negative electrode of the lithium secondary battery. At this time, the electrolytic salt dissolved in the electrolyte plays a role of stably maintaining the charging voltage of the lithium ion capacitor without generating an overvoltage.
이때, 리튬이온 캐패시터에서 음이온의 전자밀도가 너무 작은 전해염을 사용할 경우, 고율충전시 충전용량을 제대로 잡아 줄 수 없기 때문에 과전압이 걸리게 된다. 한편 전자밀도가 큰 음이온일수록 충전시 리튬이온 캐패시터의 산화전극에 강하게 흡착되어 고율 방전시 과전압을 만들어 낼 가능성이 매우 크다.In this case, when using an electrolytic salt having an electron density of anion too small in a lithium ion capacitor, an overvoltage is applied because the charging capacity cannot be properly grasped during high rate charging. On the other hand, the higher the electron density of the anion, the more strongly it is strongly adsorbed to the anode of the lithium ion capacitor during charging, the possibility of generating overvoltage during high rate discharge.
따라서, 전자밀도가 큰 음이온이 전극과 강하게 흡착되는 것을 억제시켜 고율에서도 고용량의 캐패시터를 구현할 수 있는 캐패시터의 개발이 요구되었다.Therefore, the development of a capacitor capable of realizing a high capacity capacitor even at a high rate by suppressing strong adsorption of anion with a large electron density is required.
상기 문제점을 해결하기 위해 본 발명의 목적은 전기화학 캐패시터, 리튬이온 캐패시터 등의 충방전시 불필요한 과전압을 방지하여 캐패시터의 고율충방전 특성을 향상시킬 수 있는 캐패시터용 전해질 및 이를 포함한 캐패시터를 제공하는 데 있다.In order to solve the above problems, an object of the present invention is to provide an electrolyte for a capacitor and a capacitor including the same, which can improve the high-rate charging and discharging characteristics of the capacitor by preventing unnecessary overvoltage during charging and discharging such as an electrochemical capacitor and a lithium ion capacitor. have.
상기 목적을 달성하기 위해 본 발명은 전자이동의 공명효과를 유도시킬 수 있는 하기 화학식 1 내지 화학식 11 중에서 1이상 포함된 방향족 화합물로서, 구조적으로 국부적 분극현상을 억제시킬 수 있는 위치에 관능기가 존재하며 비점이 80℃ 이상인 치환체의 유기화합물을 포함하되, 화학식 1 내지 화학식 11에서 R은 메틸, 에틸, 프로필 및 부틸의 알킬기에서 1이상 선택된 관능기인 것을 특징으로 하는 고율충방전 특성이 향상된 전해질을 제공한다.In order to achieve the above object, the present invention is an aromatic compound included in at least one of the following Chemical Formulas 1 to 11 that can induce a resonance effect of electron transfer, the functional group is present at a position that can structurally suppress local polarization phenomenon An organic compound having a boiling point of 80 ° C. or more includes a substituent, and in Formulas 1 to 11, R is an electrolyte having improved high-rate charging and discharging characteristics, wherein at least one functional group is selected from alkyl groups of methyl, ethyl, propyl, and butyl. .
[화학식 1][Formula 1]
Figure PCTKR2013001919-appb-I000001
Figure PCTKR2013001919-appb-I000001
R은 1,3에 위치, n은 2.R is located at 1,3, n is 2.
[화학식 2][Formula 2]
Figure PCTKR2013001919-appb-I000002
Figure PCTKR2013001919-appb-I000002
R은 1,4 또는 1,3,5에 위치, n은 2,3.R is located at 1,4 or 1,3,5, n is 2,3.
[화학식 3][Formula 3]
Figure PCTKR2013001919-appb-I000003
Figure PCTKR2013001919-appb-I000003
R은 1,5 또는 1,3,5,7에 위치, n은 2,4.R is located at 1,5 or 1,3,5,7, n is 2,4.
[화학식 4][Formula 4]
Figure PCTKR2013001919-appb-I000004
Figure PCTKR2013001919-appb-I000004
R은 1,6위치, 1,3,5,7위치, 1,2,7,8위치, 1,3,5,7,9위치, 1,2,3,6,7,8위치 및 1,2,3,4,6,7,8,9위치 중 어느 하나에 위치함. n은 2,4,5,6,8.R is 1,6 position, 1,3,5,7 position, 1,2,7,8 position, 1,3,5,7,9 position, 1,2,3,6,7,8 position and 1 Located at any of 2,3,4,6,7,8,9 positions. n is 2,4,5,6,8.
[화학식 5][Formula 5]
Figure PCTKR2013001919-appb-I000005
Figure PCTKR2013001919-appb-I000005
R은 1,6위치, 1,3,5,7위치, 1,2,7,8위치, 1,3,5,7,9위치, 1,2,3,6,7,8위치 및 1,2,3,4,6,7,8,9위치 중 어느 하나에 위치함. n은 2,4,5,6,8.R is 1,6 position, 1,3,5,7 position, 1,2,7,8 position, 1,3,5,7,9 position, 1,2,3,6,7,8 position and 1 Located at any of 2,3,4,6,7,8,9 positions. n is 2,4,5,6,8.
[화학식 6][Formula 6]
Figure PCTKR2013001919-appb-I000006
Figure PCTKR2013001919-appb-I000006
R은 2,4위치, 3,5위치, 3,4위치 및 2,5위치 중 어느 하나에 위치함. n은 2.R is located at any one of 2,4 position, 3,5 position, 3,4 position and 2,5 position. n is 2.
[화학식 7][Formula 7]
Figure PCTKR2013001919-appb-I000007
Figure PCTKR2013001919-appb-I000007
R은 2,4위치, 3,5위치, 3,4위치 및 2,5위치 중 어느 하나에 위치함. n은 2.R is located at any one of 2,4 position, 3,5 position, 3,4 position and 2,5 position. n is 2.
[화학식 8][Formula 8]
Figure PCTKR2013001919-appb-I000008
Figure PCTKR2013001919-appb-I000008
R은 2,4위치, 3,5위치, 3,4위치 및 2,5위치 중 어느 하나에 위치함. n은 2.R is located at any one of 2,4 position, 3,5 position, 3,4 position and 2,5 position. n is 2.
[화학식 9][Formula 9]
Figure PCTKR2013001919-appb-I000009
Figure PCTKR2013001919-appb-I000009
R은 2,4,6에 위치, n은 3.R is located at 2,4,6, n is 3.
[화학식 10][Formula 10]
Figure PCTKR2013001919-appb-I000010
Figure PCTKR2013001919-appb-I000010
R은 2,5에 위치, n은 2.R is located at 2,5, n is 2.
[화학식 11][Formula 11]
Figure PCTKR2013001919-appb-I000011
Figure PCTKR2013001919-appb-I000011
R은 2,4,6 또는 2,4,5,7에 위치, n은 3,4.R is located at 2,4,6 or 2,4,5,7 and n is 3,4.
또한 본 발명은 상기 화학식 1 내지 화학식 11에서 R은 메톡시(methoxy), 에톡시(ethoxy), 프로파녹시(propanoxy) 및 부톡시(butoxy)의 알콕시기 중에서 어느 하나의 관능기인 것을 특징으로 하는 고율충방전 특성이 향상된 전해질을 제공한다.In the present invention, in Formulas 1 to 11, R is a functional group of any one of alkoxy groups of methoxy, ethoxy, propanoxy and butoxy. It provides an electrolyte with improved high rate charge and discharge characteristics.
또한 본 발명은 상기 화학식 1 내지 화학식 11에서 R은 플루오로(fluoro), 클로로(chloro) 및 브로모(bromo) 중에서 어느 하나의 관능기인 것을 특징으로 하는 고율충방전 특성이 향상된 전해질을 제공한다.In another aspect, the present invention provides an electrolyte with improved high-rate charging and discharging characteristics, characterized in that R is any one functional group among fluoro, chloro and bromo.
또한 본 발명은 상기 화학식 1 내지 화학식 11에서 상기 알킬기에 아세틸(acetyl)기, 알데하이드(aldehyde)기, 아민(amine)기, 에스테르(ester)기, 에테르(ether)기 중 어느 하나가 포함된 것을 특징으로 하는 고율충방전 특성이 향상된 전해질을 제공한다.In addition, the present invention is that the alkyl group in Formula 1 to Formula 11 that any one of the acetyl group, aldehyde group, amine group, amine group, ester group, ether group Provided is an electrolyte having improved high rate charge / discharge characteristics.
또한 본 발명은 상기 알킬기와 구조적으로 연결된 탄소(C)에 연결되어 있는 수소(H)는 플루오로(fluoro), 클로로(chloro) 및 브로모(bromo) 중에서 어느 하나로 치환된 것을 특징으로 하는 고율충방전 특성이 향상된 전해질을 제공한다.In addition, the present invention is a high-yield characterized in that the hydrogen (H) connected to the carbon (C) structurally connected to the alkyl group is substituted with any one of fluoro (chloro), chloro (bro) and bromo (bromo) It provides an electrolyte with improved discharge characteristics.
또한 본 발명은 상기 방향족 화합물이 전해질 100중량부에 대하여 1 ~ 10 중량부를 포함하는 것을 특징으로 하는 고율충방전 특성이 향상된 전해질을 제공한다.In another aspect, the present invention provides an electrolyte with improved high rate charge and discharge characteristics, characterized in that the aromatic compound comprises 1 to 10 parts by weight based on 100 parts by weight of the electrolyte.
또한 본 발명은 전해질이 상기 방향족 화합물, 전해염 및 비수계 유기용매를 포함하는 고율충방전 특성이 향상된 전해질을 제공한다.In another aspect, the present invention provides an electrolyte with improved high rate charge and discharge characteristics, the electrolyte comprising the aromatic compound, an electrolytic salt and a non-aqueous organic solvent.
또한 본 발명은 상기 전해염이 LiPF6, LiBF4, LiTFSI, LiSbF6, LiAsF6, LiClO4, LiCF3SO3, Li(CF3SO2)2N, LiC4F9SO3, LiSbF6, LiAlO4, LiAlCl4, LiN(CxF2x+1SO2)(CyF2y+1SO2)(단, x, y는 자연수), LiCl, LiI 로 이루어진 군에서 1 이상 혼합한 것을 특징으로 하는 고율충방전 특성이 향상된 전해질을 제공한다.In the present invention, the electrolytic salt is LiPF 6 , LiBF 4 , LiTFSI, LiSbF 6 , LiAsF 6 , LiClO 4 , LiCF 3 SO 3 , Li (CF 3 SO 2 ) 2 N, LiC 4 F 9 SO 3 , LiSbF 6 , LiAlO 4 , LiAlCl 4 , LiN (C x F 2x + 1 SO 2 ) (C y F 2y + 1 SO 2 ) (where x, y is a natural number), LiCl, LiI, characterized in that at least one mixture in the group consisting of Provided is an electrolyte with improved high rate charge / discharge characteristics.
또한 본 발명은 상기 비수계 유기용매가 에틸렌 카본네이트(EC), 프로필렌 카본네이트(PC), 디메틸 카본네이트(DMC), 디에틸 카본네이트(DEC), 에틸메틸 카본 네이트(EMC), 1,2-디메톡시에텐(DME), γ-부티로락톤(BL), 테트라하이드로퓨란(THF), 1,3-디옥솔레인(DOL), 디에틸이써(DEE), 메틸 포르메이트(MF), 메틸프로피오네이트(MP), 술폴레인(S), 디메틸설폭사이드(DMSO) 및 아세토니트릴(AN)로 이루어진 군에서 1이상 혼합한 것을 특징으로 하는 고율충방전 특성이 향상된 전해질을 제공한다.In the present invention, the non-aqueous organic solvent is ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), 1,2 -Dimethoxyethene (DME), γ-butyrolactone (BL), tetrahydrofuran (THF), 1,3-dioxolane (DOL), diethylether (DEE), methyl formate (MF) It provides an improved electrolyte with high rate charging and discharging characteristics, characterized in that at least one mixture of methyl propionate (MP), sulfolane (S), dimethyl sulfoxide (DMSO) and acetonitrile (AN).
또한 본 발명은 상기 전해질을 포함하는 캐패시터를 제공한다.In another aspect, the present invention provides a capacitor comprising the electrolyte.
본 발명에 따른 전해질을 이용하여 캐패시터를 제조하는 경우, 전자밀도가 큰 음이온을 전해질염으로 사용하더라도 음이온이 전극과 강하게 흡착되는 것을 억제시키는 효과가 있다.When the capacitor is manufactured using the electrolyte according to the present invention, even when an anion having a large electron density is used as the electrolyte salt, there is an effect of suppressing the strong adsorption of the anion with the electrode.
또한 본 발명에 따른 캐패시터는 고율 충방전시에도 불필요한 과전압을 방지하여 캐패시터의 고율충방전 특성을 향상시킬 수 있는 효과가 있다.In addition, the capacitor according to the present invention has an effect of improving the high rate charge and discharge characteristics of the capacitor by preventing unnecessary overvoltage even during high rate charge and discharge.
본 명세서에서 사용되는 정도의 용어 “약”, “실질적으로” 등은 언급된 의미에 고유한 제조 및 물질 허용오차가 제시될 때 그 수치에서 또는 그 수치에 근접한 의미로 사용되고, 본 발명의 이해를 돕기 위해 정확하거나 절대적인 수치가 언급된 개시 내용을 비양심적인 침해자가 부당하게 이용하는 것을 방지하기 위해 사용된다.As used herein, the terms “about”, “substantially”, and the like, are used at, or in close proximity to, numerical values when manufacturing and material tolerances inherent in the meanings indicated are intended to aid the understanding of the invention. Accurate or absolute figures are used to assist in the prevention of unfair use by unscrupulous infringers.
본 발명자는 전자밀도가 큰 음이온을 사용한 전해질 조건하에서 용량감소 현상이 일어나는 것을 방지할 수 있는 극성이 비교적 낮은 유기용매를 개발하여 리튬이온 캐패시터 등과 같은 전기화학 캐패시터의 전해질에 첨가할 경우, 고율에서도 고용량의 캐패시터를 구현할 수 있다는 점에 착안하여 본 발명을 완성하였다.The present inventors have developed an organic solvent having a relatively low polarity that can prevent the capacity decrease from occurring under electrolyte conditions using an anion having a high electron density, and when added to an electrolyte of an electrochemical capacitor such as a lithium ion capacitor, a high capacity even at a high rate The present invention has been completed based on the fact that the capacitor can be implemented.
본 발명은 하기 화학식 1 내지 화학식 11 중에서 1이상 포함된 방향족 화합물을 포함하는 전해질인 것을 특징으로 한다. The present invention is characterized in that the electrolyte containing an aromatic compound included in at least one of the formulas (1) to (11).
[화학식 1][Formula 1]
Figure PCTKR2013001919-appb-I000012
Figure PCTKR2013001919-appb-I000012
R은 1,3에 위치, n은 2.R is located at 1,3, n is 2.
[화학식 2][Formula 2]
Figure PCTKR2013001919-appb-I000013
Figure PCTKR2013001919-appb-I000013
R은 1,4 또는 1,3,5에 위치, n은 2,3.R is located at 1,4 or 1,3,5, n is 2,3.
[화학식 3][Formula 3]
Figure PCTKR2013001919-appb-I000014
Figure PCTKR2013001919-appb-I000014
R은 1,5 또는 1,3,5,7에 위치, n은 2,4.R is located at 1,5 or 1,3,5,7, n is 2,4.
[화학식 4][Formula 4]
Figure PCTKR2013001919-appb-I000015
Figure PCTKR2013001919-appb-I000015
R은 1,6위치, 1,3,5,7위치, 1,2,7,8위치, 1,3,5,7,9위치, 1,2,3,6,7,8위치 및 1,2,3,4,6,7,8,9위치 중 어느 하나에 위치함. n은 2,4,5,6,8.R is 1,6 position, 1,3,5,7 position, 1,2,7,8 position, 1,3,5,7,9 position, 1,2,3,6,7,8 position and 1 Located at any of 2,3,4,6,7,8,9 positions. n is 2,4,5,6,8.
[화학식 5][Formula 5]
Figure PCTKR2013001919-appb-I000016
Figure PCTKR2013001919-appb-I000016
R은 1,6위치, 1,3,5,7위치, 1,2,7,8위치, 1,3,5,7,9위치, 1,2,3,6,7,8위치 및 1,2,3,4,6,7,8,9위치 중 어느 하나에 위치함. n은 2,4,5,6,8.R is 1,6 position, 1,3,5,7 position, 1,2,7,8 position, 1,3,5,7,9 position, 1,2,3,6,7,8 position and 1 Located at any of 2,3,4,6,7,8,9 positions. n is 2,4,5,6,8.
[화학식 6][Formula 6]
Figure PCTKR2013001919-appb-I000017
Figure PCTKR2013001919-appb-I000017
R은 2,4위치, 3,5위치, 3,4위치 및 2,5위치 중 어느 하나에 위치함. n은 2.R is located at any one of 2,4 position, 3,5 position, 3,4 position and 2,5 position. n is 2.
[화학식 7][Formula 7]
Figure PCTKR2013001919-appb-I000018
Figure PCTKR2013001919-appb-I000018
R은 2,4위치, 3,5위치, 3,4위치 및 2,5위치 중 어느 하나에 위치함. n은 2.R is located at any one of 2,4 position, 3,5 position, 3,4 position and 2,5 position. n is 2.
[화학식 8][Formula 8]
Figure PCTKR2013001919-appb-I000019
Figure PCTKR2013001919-appb-I000019
R은 2,4위치, 3,5위치, 3,4위치 및 2,5위치 중 어느 하나에 위치함. n은 2.R is located at any one of 2,4 position, 3,5 position, 3,4 position and 2,5 position. n is 2.
[화학식 9][Formula 9]
Figure PCTKR2013001919-appb-I000020
Figure PCTKR2013001919-appb-I000020
R은 2,4,6에 위치, n은 3.R is located at 2,4,6, n is 3.
[화학식 10][Formula 10]
Figure PCTKR2013001919-appb-I000021
Figure PCTKR2013001919-appb-I000021
R은 2,5에 위치, n은 2.R is located at 2,5, n is 2.
[화학식 11][Formula 11]
Figure PCTKR2013001919-appb-I000022
Figure PCTKR2013001919-appb-I000022
R은 2,4,6 또는 2,4,5,7에 위치, n은 3,4.R is located at 2,4,6 or 2,4,5,7 and n is 3,4.
상기 화학식 1 내지 화학식 11은 구조적으로 국부적 분극현상을 억제시킬 수 있는 위치에 관능기가 존재하며 비점이 80℃ 이상인 치환체의 유기화합물을 포함하는 데, 상기 화학식 1 내지 화학식 11을 포함한 화합물은 전자이동의 공명효과를 유도시킬 수 있다.Formula 1 to Formula 11 includes an organic compound having a functional group at a position capable of structurally suppressing local polarization and having a boiling point of 80 ° C. or more, wherein the compound including Formula 1 to Formula 11 may Resonance effect can be induced.
구조적으로 국부적 분극현상을 억제시킬 수 있는 위치에 동일한 전자공여기 또는 전자흡인기 등의 관능기가 존재하는 방향족 화합물은 국부적으로는 분극화되어 있지만, 화합물 전체적으로는 분극 특성이 없어지게 되므로 충전된 전극계면에서음이온 또는 양이온이 강하게 흡착되는 것을 억제시킬 수 있기 때문에 고율 충방전 특성이 우수한 전해질 조건을 만들어 낼 수 있게 된다.Aromatic compounds in which functional groups such as electron donor groups or electron withdrawing groups exist in a position where structural polarization can be suppressed locally are polarized locally, but the polarization characteristics of the compound as a whole are lost. Since the cation can be suppressed from being strongly adsorbed, it is possible to create electrolyte conditions with excellent high rate charge / discharge characteristics.
또한, 비점이 80℃ 미만의 유기화합물을 사용하게 될 경우, 커패시터의 고온특성이 악화되게 되므로 바람직하지 않다.In addition, when the boiling point is to use an organic compound of less than 80 ℃, it is not preferable because the high temperature characteristics of the capacitor deteriorate.
화학식 1 내지 화학식 11에서 R은 메틸, 에틸, 프로필 및 부틸의 알킬기에서 1이상 선택된 관능기일 수 있다.In formulas (1) to (11), R may be one or more functional groups selected from alkyl groups of methyl, ethyl, propyl and butyl.
또한, 선택적으로 상기 화학식 1 내지 화학식 11에서 R은 메톡시(methoxy), 에톡시(ethoxy), 프로파녹시(propanoxy) 및 부톡시(butoxy)의 알콕시기 중에서 어느 하나의 관능기일 수 있다.In addition, in Formula 1 to Formula 11, R may be any one of alkoxy groups of methoxy, ethoxy, propanoxy and butoxy.
또한, 선택적으로 상기 화학식 1 내지 화학식 11에서 R은 플루오로(fluoro), 클로로(chloro) 및 브로모(bromo) 중에서 어느 하나의 관능기일 수 있다.Also, optionally in Formula 1 to Formula 11, R may be any one functional group among fluoro, chloro, and bromo.
또한, 선택적으로 상기 화학식 1 내지 화학식 11에서 상기 알킬기에 아세틸(acetyl)기, 알데하이드(aldehyde)기, 아민(amine)기, 에스테르(ester)기, 에테르(ether)기 중 어느 하나가 포함된 관능기일 수 있다.Also, optionally, the functional group including any one of an acetyl group, an aldehyde group, an amine group, an ester group, and an ether group in the alkyl group in Formulas 1 to 11 Can be.
또한, 선택적으로 화학식 1 내지 화학식 11에서 R은 메틸, 에틸, 프로필 및 부틸의 알킬기에서 1이상 선택된 관능기이며, 상기 알킬기와 구조적으로 연결된 탄소(C)에 연결되어 있는 수소(H)가 플루오로(fluoro), 클로로(chloro) 및 브로모(bromo) 중에서 어느 하나로 치환되어 이루어질 수도 있다.In addition, in Formulas 1 to 11, R is one or more functional groups selected from alkyl groups of methyl, ethyl, propyl and butyl, and hydrogen (H) connected to carbon (C) structurally linked with the alkyl group is fluoro ( It may be substituted by any one of fluoro, chloro and bromo.
상기 화학식 1 내지 화학식 11 중 어느 하나로 이루어지는 방향족 화합물이 포함된 전해질은 전자밀도가 큰 음이온이 전극과 강하게 흡착되는 것을 억제시켜 고율에서도 고용량의 캐패시터를 구현할 수 있다.An electrolyte containing an aromatic compound made of any one of Formulas 1 to 11 may prevent a large electron density anion from being strongly adsorbed with an electrode, thereby realizing a capacitor having a high capacity even at a high rate.
상기 방향족 화합물은 전해질 100중량부에 대하여 1 ~ 10 중량부를 포함하는 것이 바람직하다.The aromatic compound preferably contains 1 to 10 parts by weight based on 100 parts by weight of the electrolyte.
상기 범위내에서는 커패시터 전극을 충방전 시킬 때 불필요한 과전압을 방지하여 커패시터의 고율특성을 향상시킬 수 있다. 상기 화합물이 1중량부 보다 적은 양을 사용할 경우 전자밀도가 큰 음이온이 전극에 강하게 흡착되어 형성되는 과전압 형성을 막을 수 없다. 10중량부 보다 많은 양을 사용할 경우에는 낮은 전자 밀도를 지닌 음이온에 대한 용량 저하를 유발시킬 수 있기 때문에 유용한 효과를 기대하기 어렵다.Within this range, unnecessary overvoltage can be prevented when charging and discharging the capacitor electrode, thereby improving the high rate characteristic of the capacitor. When the compound is used in an amount less than 1 part by weight, an anion having a large electron density cannot be prevented from being formed due to strong adsorption on the electrode. If the amount is more than 10 parts by weight, it is difficult to expect a useful effect because it can cause a decrease in capacity for the anion having a low electron density.
본 발명에 따른 전해질은 슈퍼캐패시터, 리튬이온캐패시터 등의 전기화학 캐패시터에 활용될 수 있는 데, 상기 전해질은 캐패시터를 제조할 경우, 상기 화학식 1 내지 화학식 11 중 1이상 선택된 화합물, 전해염 및 비수계 유기용매로 이루어질 수 있다.The electrolyte according to the present invention can be utilized in electrochemical capacitors such as supercapacitors, lithium ion capacitors, and the like, when the capacitor is prepared, the at least one compound selected from Chemical Formulas 1 to 11, electrolytic salts and non-aqueous systems It may consist of an organic solvent.
또한, 리튬이온 캐패시터 제조시에 사용될 수 있는 전해염으로는 LiPF6, LiBF4, LiTFSI, LiSbF6, LiAsF6, LiClO4, LiCF3SO3, Li(CF3SO2)2N, LiC4F9SO3, LiSbF6, LiAlO4, LiAlCl4, LiN(CxF2x+1SO2)(CyF2y+1SO2)(단, x, y는 자연수), LiCl, LiI 등으로 이루어진 군에서 1 이상 혼합하여 리튬이온 캐패시터용 전해질로 사용할 수 있다.In addition, the electrolytic salts that may be used in the production of lithium ion capacitors include LiPF 6 , LiBF 4 , LiTFSI, LiSbF 6 , LiAsF 6 , LiClO 4 , LiCF 3 SO 3 , Li (CF 3 SO 2 ) 2 N, LiC 4 F 9 SO 3 , LiSbF 6 , LiAlO 4 , LiAlCl 4 , LiN (C x F 2x + 1 SO 2 ) (C y F 2y + 1 SO 2 ) (where x and y are natural numbers), LiCl, LiI, etc. It can be used as an electrolyte for lithium ion capacitors by mixing at least one group.
또한, 비수계 유기용매는 에틸렌 카본네이트(EC), 프로필렌 카본네이트(PC), 디메틸 카본네이트(DMC), 디에틸 카본네이트(DEC), 에틸메틸 카본 네이트(EMC), 1,2-디메톡시에텐(DME), γ-부티로락톤(BL), 테트라하이드로퓨란(THF), 1,3-디옥솔레인(DOL), 디에틸이써(DEE), 메틸 포르메이트(MF), 메틸프로피오네이트(MP), 술폴레인(S), 디메틸설폭사이드(DMSO) 및 아세토니트릴(AN) 등으로 이루어진 군에서 1이상 혼합하여 전해질로 사용할 수 있다.In addition, the non-aqueous organic solvent is ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC), ethylmethyl carbonate (EMC), 1,2-dimethoxy Ethene (DME), γ-butyrolactone (BL), tetrahydrofuran (THF), 1,3-dioxolane (DOL), diethylether (DEE), methyl formate (MF), methylpro Pioneate (MP), sulfolane (S), dimethyl sulfoxide (DMSO) and acetonitrile (AN), etc. can be used as an electrolyte by mixing at least one.
상기와 같은 전해질을 이용하여 캐패시터를 제조하는 경우, 전자밀도가 큰 음이온을 전해질염으로 사용하더라도 음이온이 전극과 강하게 흡착되는 것을 억제시키는 효과가 있다. 따라서, 고율 충방전시에도 과전압이 걸리지 않게 되어 고용량의 캐패시터를 구현할 수 있다.When the capacitor is manufactured using the electrolyte as described above, even if an anion having a large electron density is used as the electrolyte salt, there is an effect of suppressing the strong adsorption of the anion with the electrode. Therefore, overvoltage is not applied even at high rate charging and discharging, so that a capacitor having a high capacity can be realized.
한편, 본 발명에 따른 캐패시터는 양극, 음극, 세퍼레이터 및 상술한 전해질을 포함하는 캐패시터를 제공한다.On the other hand, the capacitor according to the present invention provides a capacitor including the positive electrode, the negative electrode, the separator and the electrolyte described above.
상기 양극의 전극 합재로는 양극 활물질, 도전재 및 바인더를 포함하여 구성되며, 음극의 전극 합재로는 음극 활물질, 도전재 및 바인더를 포함하여 구성된다.The electrode mixture of the positive electrode includes a positive electrode active material, a conductive material and a binder, and the electrode mixture of the negative electrode includes a negative electrode active material, a conductive material and a binder.
상기 양극 활물질로는 이중층 용량을 가지는 모든 탄소 재료가 가능하고, 활성탄, 천연섬유, 비정질 카본, 플라렌(fullerene), 나노 튜브 및 그래핀 (graphene) 등으로 이루어진 군에서 1 이상 사용할 수 있으며, 특별히 그 종류에 제한되지 않지만 비표면적이 크고 값싼 활성탄을 사용하는 것이 바람직하다.The cathode active material may be any carbon material having a double layer capacity, and may be used in the group consisting of activated carbon, natural fiber, amorphous carbon, fullerene, nanotube, graphene, and the like. Although it is not limited to the kind, it is preferable to use activated carbon with a large specific surface area and cheap.
상기 음극 활물질로는 리튬 이온과 흡착과 탈리가 가능한 모든 탄소 재료를 사용할 수 있으며, 예를 들어, 천연흑연, 인조흑연, 혼연화 메소카본, 혼연화 탄소섬유, 코코스, 피치 등을 열처리한 탄소재료, 하드카본, 소프트 카본 등을 이용할 수 있다.As the negative electrode active material, any carbon material capable of adsorption and desorption with lithium ions may be used, and for example, natural graphite, artificial graphite, mixed mesocarbon, mixed carbon fiber, cocos, carbon material heat treated, etc. , Hard carbon, soft carbon and the like can be used.
상기 도전재로서는 구체적으로 그래파이트, 카본블랙, 아세틸렌 블랙을, 케첸 블랙 등을 이용할 수 있다.Specifically as the conductive material, graphite, carbon black, acetylene black, Ketjen black, or the like can be used.
상기 바인더로는 폴리에틸렌, 폴리프로필렌, 폴리에틸렌 테레프탈레이트, 방향족 폴리아미드, 셀롤로오스, 스타이렌-부타다이엔 고무 등을 사용할 수 있으며, 전해액에 대하여 안정적인 재료라면 크게 제한되지 않는다.As the binder, polyethylene, polypropylene, polyethylene terephthalate, aromatic polyamide, cellulose, styrene-butadiene rubber, or the like may be used, and the material is not particularly limited as long as it is a stable material for electrolyte.
또한, 상기 세퍼레이트는 양극과 음극 사이에 위치하여 두 극판 활물질의 접촉에 의한 단락을 방지하고 전지반응에 필요한 전해액을 보유, 유지한다. 상기 세퍼레이트로는 절연성이 있으며 비수전해액을 침투시킬 수 있는 것이면 특별히 제한되지 않는다. 구체적인 예로는 폴리에틸렌, 비닐론, 폴리아미드, 폴리프로필렌, 폴리비닐클로라이드 및 폴리에틸렌 등의 소재로 공극 또는 기공을 가지는 다공질 재료이면 사용가능하다.In addition, the separator is located between the positive electrode and the negative electrode to prevent a short circuit caused by the contact between the two electrode plate active material and to hold and maintain the electrolyte solution required for the battery reaction. The separator is not particularly limited as long as it is insulating and can penetrate the nonaqueous electrolyte. Specific examples thereof include polyethylene, vinylon, polyamide, polypropylene, polyvinyl chloride, polyethylene, and other porous materials having pores or pores.
이하, 본 발명의 실시예에 대하여 상세히 설명한다.Hereinafter, embodiments of the present invention will be described in detail.
실시예 1Example 1
전해질의 제조는 에틸렌 카보네이트(EC):디에틸 카보네이트(DEC)를 30 : 70의 부피비로 혼합한 유기용매 및 0.5M LiBF4 에 화학식 2인 벤젠이고, n이 2로 이루어지며, 1,4위치에 플루오로(fluoro)가 형성된 방향족 화합물을 혼합하여 전해질을 제조하였다. 상기 방향족 화합물은 전해질 100중량부에 대하여 1중량부로 첨가하였다.The preparation of the electrolyte is an organic solvent in which ethylene carbonate (EC): diethyl carbonate (DEC) is mixed in a volume ratio of 30:70 and benzene of the formula (2) in 0.5M LiBF 4 , where n is 2, and 1,4-position An electrolyte was prepared by mixing aromatic compounds in which fluoro was formed. The aromatic compound was added in 1 part by weight based on 100 parts by weight of the electrolyte.
캐패시터의 제조는 당해 업계에서 알려진 통상적인 방법으로 제조하였는 데, 활성탄과 리튬 금속을 적당한 크기로 자른 뒤, 이들 사이에 폴리에틸레 다공성 필름으로 제조된 세퍼레이터를 삽입하여 전극 조립체를 제조하였다. 이 전극 조립체를 파우치에 삽입한 후 전해액 주입구를 제외한 부분을 융착시키고, 제조된 전해질을 주입하여 주입구에 넣어 캐패시터를 완성하였다.Capacitors were manufactured by conventional methods known in the art, in which activated carbon and lithium metal were cut to a suitable size, and a separator made of a porous polyethylene film was inserted therebetween to prepare an electrode assembly. After inserting the electrode assembly into the pouch, the portion except the electrolyte injection hole was fused, and the prepared electrolyte was injected into the injection hole to complete the capacitor.
실시예 2 및 3Examples 2 and 3
실시예1과 각각 동일하게 실시하되, 방향족 화합물은 전해질 100중량부에 대하여 5중량부(실시예2), 10중량부(실시예3)로 첨가하였다.In the same manner as in Example 1, the aromatic compound was added in 5 parts by weight (Example 2) and 10 parts by weight (Example 3) based on 100 parts by weight of the electrolyte.
실시예 4Example 4
실시예1과 동일하게 실시하되,Same as Example 1,
방향족 화합물은 화학식 2인 벤젠이고, n이 2로 이루어지며, 1,4위치에 에틸기가 형성된 방향족 화합물을 혼합하여 전해질을 제조하였다. 상기 방향족 화합물은 전해질 100중량부에 대하여 1중량부로 첨가하였다.The aromatic compound is benzene represented by Chemical Formula 2, n is 2, and an electrolyte is prepared by mixing an aromatic compound in which an ethyl group is formed at 1,4 positions. The aromatic compound was added in 1 part by weight based on 100 parts by weight of the electrolyte.
실시예 5 및 6Examples 5 and 6
실시예 4와 각각 동일하게 실시하되, 방향족 화합물은 전해질 100중량부에 대하여 5중량부(실시예5), 10중량부(실시예6)로 첨가하였다.In the same manner as in Example 4, the aromatic compound was added in 5 parts by weight (Example 5) and 10 parts by weight (Example 6) based on 100 parts by weight of the electrolyte.
실시예 7Example 7
실시예1과 동일하게 실시하되,Same as Example 1,
방향족 화합물은 화학식 6인 피롤(pyrrole)이고, n이 2로 이루어지며, 2,4위치에 메톡시기가 형성된 방향족 화합물을 혼합하여 전해질을 제조하였다. 상기 방향족 화합물은 전해질 100중량부에 대하여 1중량부로 첨가하였다.The aromatic compound is pyrrole (Formula 6), n is composed of 2, an electrolyte was prepared by mixing an aromatic compound having a methoxy group formed at 2,4 positions. The aromatic compound was added in 1 part by weight based on 100 parts by weight of the electrolyte.
실시예 8 및 9Examples 8 and 9
실시예 7와 각각 동일하게 실시하되, 방향족 화합물은 전해질 100중량부에 대하여 5중량부(실시예8), 10중량부(실시예9)로 첨가하였다.In the same manner as in Example 7, the aromatic compound was added in 5 parts by weight (Example 8) and 10 parts by weight (Example 9) based on 100 parts by weight of the electrolyte.
실시예 10Example 10
실시예1과 동일하게 실시하되,Same as Example 1,
방향족 화합물은 화학식 6인 피롤(pyrrole)이고, n이 2로 이루어지며, 2,4위치에 메톡시기가 형성된 방향족 화합물을 혼합하여 전해질을 제조하였다. 상기 방향족 화합물은 전해질 100중량부에 대하여 1중량부로 첨가하였다.The aromatic compound is pyrrole (Formula 6), n is composed of 2, an electrolyte was prepared by mixing an aromatic compound having a methoxy group formed at 2,4 positions. The aromatic compound was added in 1 part by weight based on 100 parts by weight of the electrolyte.
실시예 11 및 12Examples 11 and 12
실시예 10과 각각 동일하게 실시하되, 방향족 화합물은 전해질 100중량부에 대하여 5중량부(실시예11), 10중량부(실시예12)첨가하였다.In the same manner as in Example 10, the aromatic compound was added 5 parts by weight (Example 11) and 10 parts by weight (Example 12) based on 100 parts by weight of the electrolyte.
실시예 13Example 13
실시예1과 동일하게 실시하되,Same as Example 1,
방향족 화합물은 화학식 7인 퓨란(furan)이고, n이 2로 이루어지며, 2,4위치에 플루오로(fluoro)가 형성된 방향족 화합물을 혼합하여 전해질을 제조하였다. 상기 방향족 화합물은 전해질 100중량부에 대하여 1중량부로 첨가하였다.The aromatic compound is a furan (furan) of the general formula (7), n is composed of 2, an electrolyte was prepared by mixing an aromatic compound in which fluoro (fluoro) is formed in 2,4 positions. The aromatic compound was added in 1 part by weight based on 100 parts by weight of the electrolyte.
실시예 14 및 15Examples 14 and 15
실시예 13과 각각 동일하게 실시하되, 방향족 화합물은 전해질 100중량부에 대하여 5중량부(실시예 14), 10중량부(실시예 15)로 첨가하였다.In the same manner as in Example 13, the aromatic compound was added in 5 parts by weight (Example 14) and 10 parts by weight (Example 15) based on 100 parts by weight of the electrolyte.
실시예 16Example 16
실시예1과 동일하게 실시하되,Same as Example 1,
방향족 화합물은 화학식 10인 시클로펜타디엔이고, n이 2로 이루어지며, 2,5위치에 에틸기가 형성된 방향족 화합물을 혼합하여 전해질을 제조하였다. 상기 방향족 화합물은 전해질 100중량부에 대하여 1중량부로 첨가하였다.The aromatic compound is cyclopentadiene represented by Chemical Formula 10, n is 2, and an electrolyte is prepared by mixing an aromatic compound in which an ethyl group is formed at 2,5 positions. The aromatic compound was added in 1 part by weight based on 100 parts by weight of the electrolyte.
실시예 17 및 18Examples 17 and 18
실시예 16과 각각 동일하게 실시하되, 방향족 화합물은 전해질 100중량부에 대하여 5중량부(실시예17), 10중량부(실시예18)로 첨가하였다.In the same manner as in Example 16, the aromatic compound was added in 5 parts by weight (Example 17) and 10 parts by weight (Example 18) based on 100 parts by weight of the electrolyte.
비교예 1Comparative Example 1
실시예1과 동일하게 실시하되,Same as Example 1,
전해질의 제조는 에틸렌 카보네이트(EC):디에틸 카보네이트(DEC)를 30 : 70의 부피비로 혼합한 유기용매 및 0.5M LiBF4 만을 혼합하여 전해질을 제조하였다.In preparing the electrolyte, an electrolyte was prepared by mixing an organic solvent and 0.5 M LiBF 4 mixed with ethylene carbonate (EC): diethyl carbonate (DEC) in a volume ratio of 30:70.
상기 실시예 및 비교예로 제조된 캐패시터를 이용하여 0.2C, 1C, 2C, 5C 및 10C을 충전 후에 방전용량을 측정하였다. 측정된 결과는 아래 표 1과 같다.Discharge capacities were measured after charging 0.2C, 1C, 2C, 5C, and 10C using the capacitors prepared in Examples and Comparative Examples. The measured results are shown in Table 1 below.
표 1
구분 화합물 화합물함량(중량부) 방전용량(mAh/g)
0.2C 1C 2C 5C 10C
실시예 1 1,4-플로오르벤젠 1 76 74 65 58 47
실시예 2 5 74 70 62 56 45
실시예 3 10 72 68 60 54 49
실시예 4 1,4-에틸벤젠 1 77 74 66 58 46
실시예 5 5 73 69 60 54 44
실시예 6 10 73 68 58 49 43
실시예 7 2,4-메톡시피롤 1 74 64 56 46 42
실시예 8 5 68 60 52 44 38
실시예 9 10 67 60 53 45 39
실시예 10 2,4-메톡시티오펜 1 73 67 52 46 40
실시예 11 5 72 68 57 48 41
실시예 12 10 70 66 56 45 39
실시예 13 2,4-플로오르퓨란 1 72 68 60 57 46
실시예 14 5 70 65 58 50 42
실시예 15 10 69 62 54 46 40
실시예 16 2,5-에틸시클로펜타디엔 1 76 68 58 49 41
실시예 17 5 74 67 56 48 39
실시예 18 10 73 64 55 48 39
비교예 1 - - 75 65 52 37 23
Table 1
division compound Compound content (parts by weight) Discharge Capacity (mAh / g)
0.2C 1C 2C 5C 10C
Example 1 1,4-fluorobenzene One 76 74 65 58 47
Example 2 5 74 70 62 56 45
Example 3 10 72 68 60 54 49
Example 4 1,4-ethylbenzene One 77 74 66 58 46
Example 5 5 73 69 60 54 44
Example 6 10 73 68 58 49 43
Example 7 2,4-methoxypyrrole One 74 64 56 46 42
Example 8 5 68 60 52 44 38
Example 9 10 67 60 53 45 39
Example 10 2,4-methoxythiophene One 73 67 52 46 40
Example 11 5 72 68 57 48 41
Example 12 10 70 66 56 45 39
Example 13 2,4-fluorofuran One 72 68 60 57 46
Example 14 5 70 65 58 50 42
Example 15 10 69 62 54 46 40
Example 16 2,5-ethylcyclopentadiene One 76 68 58 49 41
Example 17 5 74 67 56 48 39
Example 18 10 73 64 55 48 39
Comparative Example 1 - - 75 65 52 37 23
실험결과 본 발명에 따른 화합물이 포함된 전해질을 이용하여 캐패시터를 제조한 경우 방전용량이 비교예 1에 비해 우수함을 확인할 수 있었다. 특히, 고율 충방전시에는 비교예 1의 경우 방전 용량이 현저히 감소하는 것에 비해 실시예 1 ~ 실시예 15는 방전용량의 감소가 크지 않음을 확인할 수 있었다.As a result, when the capacitor was prepared using the electrolyte containing the compound according to the present invention, it was confirmed that the discharge capacity was superior to that of Comparative Example 1. In particular, in the case of high rate charging and discharging, it was confirmed that in Example 1 to Example 15, the decrease in the discharge capacity was not large compared to that in the case of Comparative Example 1 significantly reduced.
이를 통해 고용량을 충방전하더라도 과전압이 걸리지 않게 되어 고용량의 캐패시터를 구현할 수 있는 효과가 있음을 확인할 수 있었다.Through this, even when charging and discharging a high capacity, it is confirmed that there is an effect that can implement a high capacity capacitor is not overvoltage.
이상에서 설명한 본 발명은 전술한 실시예에 의해 한정되는 것은 아니고, 본 발명의 기술적 사상을 벗어나지 않는 범위 내에서 여러 가지 치환, 변형 및 변경이 가능함은 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자에게 있어서 명백할 것이다.The present invention described above is not limited to the above-described embodiment, and various substitutions, modifications, and changes can be made without departing from the technical spirit of the present invention. It will be obvious to him.

Claims (10)

  1. 전자이동의 공명효과를 유도시킬 수 있는 하기 화학식 1 내지 화학식 11 중에서 1이상 포함된 방향족 화합물로서, 구조적으로 국부적 분극현상을 억제시킬 수 있는 위치에 관능기가 존재하며 비점이 80℃ 이상인 치환체의 유기화합물을 포함하되,An aromatic compound containing at least one of the following Chemical Formulas 1 to 11, which may induce a resonance effect of electron transfer, and has a functional group at a position capable of structurally suppressing local polarization and an organic compound of a substituent having a boiling point of 80 ° C or higher. Including,
    화학식 1 내지 화학식 11에서 R은 메틸, 에틸, 프로필 및 부틸의 알킬기에서 1이상 선택된 관능기인 것을 특징으로 하는 고율충방전 특성이 향상된 전해질.In Formulas 1 to 11, R is an electrolyte having high charge and discharge characteristics, characterized in that at least one functional group selected from alkyl groups of methyl, ethyl, propyl and butyl.
    [화학식 1][Formula 1]
    Figure PCTKR2013001919-appb-I000023
    Figure PCTKR2013001919-appb-I000023
    R은 1,3에 위치, n은 2.R is located at 1,3, n is 2.
    [화학식 2][Formula 2]
    Figure PCTKR2013001919-appb-I000024
    Figure PCTKR2013001919-appb-I000024
    R은 1,4 또는 1,3,5에 위치, n은 2,3.R is located at 1,4 or 1,3,5, n is 2,3.
    [화학식 3][Formula 3]
    Figure PCTKR2013001919-appb-I000025
    Figure PCTKR2013001919-appb-I000025
    R은 1,5 또는 1,3,5,7에 위치, n은 2,4.R is located at 1,5 or 1,3,5,7, n is 2,4.
    [화학식 4][Formula 4]
    Figure PCTKR2013001919-appb-I000026
    Figure PCTKR2013001919-appb-I000026
    R은 1,6위치, 1,3,5,7위치, 1,2,7,8위치, 1,3,5,7,9위치, 1,2,3,6,7,8위치 및 1,2,3,4,6,7,8,9위치 중 어느 하나에 위치함. n은 2,4,5,6,8.R is 1,6 position, 1,3,5,7 position, 1,2,7,8 position, 1,3,5,7,9 position, 1,2,3,6,7,8 position and 1 Located at any of 2,3,4,6,7,8,9 positions. n is 2,4,5,6,8.
    [화학식 5][Formula 5]
    Figure PCTKR2013001919-appb-I000027
    Figure PCTKR2013001919-appb-I000027
    R은 1,6위치, 1,3,5,7위치, 1,2,7,8위치, 1,3,5,7,9위치, 1,2,3,6,7,8위치 및 1,2,3,4,6,7,8,9위치 중 어느 하나에 위치함. n은 2,4,5,6,8.R is 1,6 position, 1,3,5,7 position, 1,2,7,8 position, 1,3,5,7,9 position, 1,2,3,6,7,8 position and 1 Located at any of 2,3,4,6,7,8,9 positions. n is 2,4,5,6,8.
    [화학식 6][Formula 6]
    Figure PCTKR2013001919-appb-I000028
    Figure PCTKR2013001919-appb-I000028
    R은 2,4위치, 3,5위치, 3,4위치 및 2,5위치 중 어느 하나에 위치함. n은 2.R is located at any one of 2,4 position, 3,5 position, 3,4 position and 2,5 position. n is 2.
    [화학식 7][Formula 7]
    Figure PCTKR2013001919-appb-I000029
    Figure PCTKR2013001919-appb-I000029
    R은 2,4위치, 3,5위치, 3,4위치 및 2,5위치 중 어느 하나에 위치함. n은 2.R is located at any one of 2,4 position, 3,5 position, 3,4 position and 2,5 position. n is 2.
    [화학식 8][Formula 8]
    Figure PCTKR2013001919-appb-I000030
    Figure PCTKR2013001919-appb-I000030
    R은 2,4위치, 3,5위치, 3,4위치 및 2,5위치 중 어느 하나에 위치함. n은 2.R is located at any one of 2,4 position, 3,5 position, 3,4 position and 2,5 position. n is 2.
    [화학식 9][Formula 9]
    Figure PCTKR2013001919-appb-I000031
    Figure PCTKR2013001919-appb-I000031
    R은 2,4,6에 위치, n은 3.R is located at 2,4,6, n is 3.
    [화학식 10][Formula 10]
    Figure PCTKR2013001919-appb-I000032
    Figure PCTKR2013001919-appb-I000032
    R은 2,5에 위치, n은 2.R is located at 2,5, n is 2.
    [화학식 11][Formula 11]
    Figure PCTKR2013001919-appb-I000033
    Figure PCTKR2013001919-appb-I000033
    R은 2,4,6 또는 2,4,5,7에 위치, n은 3,4.R is located at 2,4,6 or 2,4,5,7 and n is 3,4.
  2. 제1항에 있어서,The method of claim 1,
    상기 화학식 1 내지 화학식 11에서 R은 메톡시(methoxy), 에톡시(ethoxy), 프로파녹시(propanoxy) 및 부톡시(butoxy)의 알콕시기 중에서 어느 하나의 관능기인 것을 특징으로 하는 고율충방전 특성이 향상된 전해질.In Formulas 1 to 11, R is a high-rate charge-discharge characteristic, characterized in that any one of alkoxy groups of methoxy, ethoxy, propanoxy and butoxy alkoxy group This enhanced electrolyte.
  3. 제1항에 있어서,The method of claim 1,
    상기 화학식 1 내지 화학식 11에서 R은 플루오로(fluoro), 클로로(chloro) 및 브로모(bromo) 중에서 어느 하나의 관능기인 것을 특징으로 하는 고율충방전 특성이 향상된 전해질.In Chemical Formulas 1 to 11, R is an electrolyte having high charge / discharge characteristics, characterized in that any one of fluoro, chloro, and bromo functional groups.
  4. 제1항에 있어서,The method of claim 1,
    상기 화학식 1 내지 화학식 11에서 상기 알킬기에 아세틸(acetyl)기, 알데하이드(aldehyde)기, 아민(amine)기, 에스테르(ester)기, 에테르(ether)기 중 어느 하나가 포함된 것을 특징으로 하는 고율충방전 특성이 향상된 전해질.In the formula 1 to Formula 11, the alkyl group has a high rate, characterized in that any one of an acetyl group, an aldehyde group, an amine group, an ester group, an ether group Electrolyte with improved charge and discharge characteristics.
  5. 제1항에 있어서,The method of claim 1,
    상기 알킬기와 구조적으로 연결된 탄소(C)에 연결되어 있는 수소(H)는 플루오로(fluoro), 클로로(chloro) 및 브로모(bromo) 중에서 어느 하나로 치환된 것을 특징으로 하는 고율충방전 특성이 향상된 전해질.Hydrogen (H) connected to the carbon (C) structurally connected to the alkyl group is improved in high rate charge and discharge characteristics, characterized in that substituted with any one of fluoro (chloro), chloro (bro) and bromo (bromo) Electrolyte.
  6. 제1항 내지 제5항 중 어느 한 항에 있어서,The method according to any one of claims 1 to 5,
    상기 방향족 화합물은 전해질 100중량부에 대하여 1 ~ 10 중량부를 포함하는 것을 특징으로 하는 고율충방전 특성이 향상된 전해질.The aromatic compound has improved high rate charge and discharge characteristics, characterized in that it comprises 1 to 10 parts by weight based on 100 parts by weight of the electrolyte.
  7. 제1항 내지 제5항 중 어느 한 항에 있어서,The method according to any one of claims 1 to 5,
    전해질은 상기 방향족 화합물, 전해염 및 비수계 유기용매를 포함하는 고율충방전 특성이 향상된 전해질.Electrolyte is an electrolyte with improved high-rate charging and discharging characteristics comprising the aromatic compound, an electrolytic salt and a non-aqueous organic solvent.
  8. 제7항에 있어서,The method of claim 7, wherein
    상기 전해염은 LiPF6, LiBF4, LiTFSI, LiSbF6, LiAsF6, LiClO4, LiCF3SO3, Li(CF3SO2)2N, LiC4F9SO3, LiSbF6, LiAlO4, LiAlCl4, LiN(CxF2x+1SO2)(CyF2y+1SO2)(단, x, y는 자연수), LiCl, LiI 로 이루어진 군에서 1 이상 혼합한 것을 특징으로 하는 고율충방전 특성이 향상된 전해질.The electrolytic salt is LiPF 6 , LiBF 4 , LiTFSI, LiSbF 6 , LiAsF 6 , LiClO 4 , LiCF 3 SO 3 , Li (CF 3 SO 2 ) 2 N, LiC 4 F 9 SO 3 , LiSbF 6 , LiAlO 4 , LiAlCl 4 , LiN (C x F 2x + 1 SO 2 ) (C y F 2y + 1 SO 2 ) (where x, y is a natural number), a high rate insect characterized in that the mixture of one or more from the group consisting of LiCl, LiI Electrolyte with improved discharge characteristics.
  9. 제7항에 있어서,The method of claim 7, wherein
    상기 비수계 유기용매는 에틸렌 카본네이트(EC), 프로필렌 카본네이트(PC), 디메틸 카본네이트(DMC), 디에틸 카본네이트(DEC), 에틸메틸 카본 네이트(EMC), 1,2-디메톡시에텐(DME), γ-부티로락톤(BL), 테트라하이드로퓨란(THF), 1,3-디옥솔레인(DOL), 디에틸이써(DEE), 메틸 포르메이트(MF), 메틸프로피오네이트(MP), 술폴레인(S), 디메틸설폭사이드(DMSO) 및 아세토니트릴(AN)로 이루어진 군에서 1이상 혼합한 것을 특징으로 하는 고율충방전 특성이 향상된 전해질.The non-aqueous organic solvent is ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), 1,2-dimethoxy Ten (DME), γ-butyrolactone (BL), tetrahydrofuran (THF), 1,3-dioxolane (DOL), diethylether (DEE), methyl formate (MF), methylpropio Nate (MP), sulfolane (S), dimethyl sulfoxide (DMSO) and acetonitrile (AN) in the group consisting of at least one mixed electrolyte, characterized in that the high rate charge and discharge characteristics improved.
  10. 제1항 내지 제5항 중 어느 한 항에 의한 전해질을 포함하는 캐패시터.A capacitor comprising the electrolyte according to any one of claims 1 to 5.
PCT/KR2013/001919 2012-03-30 2013-03-11 Electrolyte having enhanced high-rate charge/discharge properties and capacitor comprising same WO2013147435A1 (en)

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