KR102239772B1 - Electrolyte additives for secondary battery and electrolyte for secondary battery including the same - Google Patents

Electrolyte additives for secondary battery and electrolyte for secondary battery including the same Download PDF

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KR102239772B1
KR102239772B1 KR1020170051803A KR20170051803A KR102239772B1 KR 102239772 B1 KR102239772 B1 KR 102239772B1 KR 1020170051803 A KR1020170051803 A KR 1020170051803A KR 20170051803 A KR20170051803 A KR 20170051803A KR 102239772 B1 KR102239772 B1 KR 102239772B1
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carbonate
electrolyte
secondary battery
battery
additive
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KR20180118452A (en
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신정주
박대운
하재민
방지민
고종관
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에스케이케미칼 주식회사
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0568—Liquid materials characterised by the solutes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0569—Liquid materials characterised by the solvents
    • 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
    • Y02E60/10—Energy storage using batteries

Abstract

본 발명은 이차전지용 전해액 첨가제 및 이를 포함하는 이차전지용 전해액에 관한 것으로서, 상기 이차전지용 전해액 첨가제는 전지 충·방전시 전지 내 계면 저항을 낮춰 전지의 출력 성능을 개선시킬 수 있고, 고온 및 저온의 사용환경에서도 출력 특성을 유지시킬 수 있다.The present invention relates to an electrolyte additive for a secondary battery and an electrolyte for a secondary battery containing the same, wherein the electrolyte additive for a secondary battery can improve the output performance of a battery by lowering the interfacial resistance in the battery during battery charging and discharging, and the use of high and low temperatures. Output characteristics can be maintained even in the environment.

Description

이차전지용 전해액 첨가제 및 이를 포함하는 이차전지용 전해액{ELECTROLYTE ADDITIVES FOR SECONDARY BATTERY AND ELECTROLYTE FOR SECONDARY BATTERY INCLUDING THE SAME}Electrolyte additive for secondary battery and electrolyte for secondary battery containing the same {ELECTROLYTE ADDITIVES FOR SECONDARY BATTERY AND ELECTROLYTE FOR SECONDARY BATTERY INCLUDING THE SAME}

본 발명은 이차전지용 전해액 첨가제 및 이를 포함하는 이차전지용 전해액에 관한 것으로서, 상기 이차전지용 전해액 첨가제는 전지 충·방전시 전지 내 계면 저항을 낮춰 전지의 출력 성능을 개선시킬 수 있고, 고온 및 저온의 사용환경에서도 출력 특성을 유지시킬 수 있다.The present invention relates to an electrolyte additive for a secondary battery and an electrolyte for a secondary battery containing the same, wherein the electrolyte additive for a secondary battery can improve the output performance of a battery by lowering the interfacial resistance in the battery during battery charging and discharging, and the use of high and low temperatures. Output characteristics can be maintained even in the environment.

모바일 기기 및 전기자동차 등 다양한 분야에서 사용되고 있는 리튬 이차전지는 리튬 이온을 흡장 및 방출하는 탄소재 등의 음극, 리튬 함유 산화물 등으로 된 양극 및 혼합 유기용매에 리튬염이 적당량 용해된 비수계 전해액으로 구성되어 있다.Lithium secondary batteries, which are used in various fields such as mobile devices and electric vehicles, are non-aqueous electrolytes in which an appropriate amount of lithium salt is dissolved in an appropriate amount of a mixed organic solvent, a negative electrode such as a carbon material that absorbs and releases lithium ions, a positive electrode made of lithium-containing oxide, etc. Consists of.

이러한 이차전지용 전해액에 첨가되어 이차전지의 출력 또는 수명 개선을 목적으로 하는 다수의 첨가제가 공지되어 있다. 예컨대, 일본등록특허 제3907446호 및 대한민국 공개특허 제 10-2013-0102969 호는 각각 리튬 옥살라토 붕산염 및 리튬 옥살라토 인산염 첨가제를 개시하고 있다. 또한, 대한민국 공개특허 제 10-2015-0050493 호는 전해액에 에틸렌 설페이트를 첨가하여 고온 및 저온에서 전지의 출력개선하고 있으며, 대한민국 공개특허 제 10-2015-0050082 호는 설피닐기를 포함하는 첨가제를 전해액에 첨가하여 전지의 사이클 수명을 개선하고 있다.A number of additives are known that are added to the electrolyte for a secondary battery to improve the output or life of the secondary battery. For example, Japanese Patent No. 3997446 and Korean Patent Laid-Open No. 10-2013-0102969 disclose lithium oxalato borate and lithium oxalato phosphate additives, respectively. In addition, Korean Patent Laid-Open No. 10-2015-0050493 adds ethylene sulfate to the electrolyte to improve the output of the battery at high and low temperatures, and Korean Patent Laid-Open No. 10-2015-0050082 uses an additive containing a sulfinyl group as an electrolyte. In addition to improving the cycle life of the battery.

그러나, 전기자동차용 전지 및 전동공구용 전지의 경우, 순간적으로 필요한 전류량을 충분히 확보하기 위한 전지의 출력특성을 향상시킬 수 있는 이차전지용 전해액 첨가제의 연구개발이 지속적으로 필요한 실정이다.However, in the case of batteries for electric vehicles and batteries for power tools, there is a need for continuous research and development of electrolyte additives for secondary batteries that can improve the output characteristics of batteries to sufficiently secure the amount of electric current required instantaneously.

이에, 본 발명자는 상술한 종래 기술의 문제점 해결 및 보다 향상된 출력특성 개선 연구를 지속적으로 수행한 결과, 이차전지의 출력특성을 개선시킬 수 있는 화합물을 발견하고, 이차전지용 전해액에 적용함으로써 본 발명을 완성하였다.Accordingly, the inventors of the present invention found a compound capable of improving the output characteristics of a secondary battery as a result of continuously conducting research on solving the problems of the above-described conventional technology and improving the output characteristics, and applying the present invention to an electrolyte solution for a secondary battery. Completed.

일본등록특허 제3907446호Japanese Patent Registration No. 39974464 대한민국 공개특허 제 10-2013-0102969 호Republic of Korea Patent Publication No. 10-2013-0102969 대한민국 공개특허 제 10-2015-0050493 호Republic of Korea Patent Publication No. 10-2015-0050493 대한민국 공개특허 제 10-2015-0050082 호Republic of Korea Patent Publication No. 10-2015-0050082

따라서, 본 발명의 목적은 이차전지용 전해액에 포함되어 전지의 계면저항을 낮춰 출력특성을 개선시킬 수 있는 이차전지용 전해액 첨가제를 제공하는 것이다.Accordingly, an object of the present invention is to provide an electrolyte solution additive for a secondary battery capable of improving output characteristics by lowering the interface resistance of the battery by being included in the electrolyte solution for a secondary battery.

본 발명의 다른 목적은 상기 이차전지용 전해액 첨가제를 포함하여 고온 및 저온 환경에서도 출력 특성이 안정적으로 유지되는 이차전지용 전해액을 제공하는 것이다.Another object of the present invention is to provide an electrolyte for a secondary battery, including the electrolyte additive for a secondary battery, in which output characteristics are stably maintained even in high and low temperature environments.

상기 목적을 달성하기 위해, 본 발명은 하기 화학식 1의 구조를 갖는 이차 전지용 전해액 첨가제를 제공한다:In order to achieve the above object, the present invention provides an electrolyte solution additive for a secondary battery having the structure of the following formula (1):

Figure 112017039529448-pat00001
Figure 112017039529448-pat00001

상기 다른 목적을 달성하기 위해, 본 발명은 비수계 용매; 리튬염; 및 하기 화학식 1의 구조를 갖는 첨가제;를 포함하는, 이차전지용 전해액을 제공한다:In order to achieve the above other object, the present invention is a non-aqueous solvent; Lithium salt; And it provides an electrolyte for a secondary battery containing;

[화학식 1][Formula 1]

Figure 112017039529448-pat00002
.
Figure 112017039529448-pat00002
.

상기 또 다른 목적을 달성하기 위해, 본 발명은 상술한 바와 같은 이차전지용 전해액을 포함하는, 이차전지를 제공한다.In order to achieve the above another object, the present invention provides a secondary battery comprising the electrolyte for a secondary battery as described above.

본 발명의 이차전지용 전해액 첨가제는 전해액에 포함되어 전지의 방전시 전극 계면의 저항을 낮추는 효과가 있으며, 이를 포함하는 이차전지는 저온에서도 안정적인 충·방전 용량보존 특성을 갖는다.The electrolyte additive for a secondary battery of the present invention is included in the electrolyte and has the effect of lowering the resistance of the electrode interface when discharging the battery, and the secondary battery including the same has a stable charge/discharge capacity preservation characteristic even at low temperatures.

본 발명에 따른 이차전지용 전해액 첨가제는 전지, 특히 전극의 계면 저항을 낮추고 고온 및 저온 환경에서 저항의 증가를 억제함으로써 출력 성능을 개선하기 위한 것으로서, 하기 화학식 1의 구조를 갖는다:The electrolyte additive for a secondary battery according to the present invention is for improving output performance by lowering the interface resistance of a battery, particularly an electrode, and suppressing an increase in resistance in high and low temperature environments, and has a structure of the following formula (1):

[화학식 1][Formula 1]

Figure 112017039529448-pat00003
.
Figure 112017039529448-pat00003
.

상기 화학식 1의 구조를 갖는 첨가제는 이환형 탄산 에스테르 구조를 갖는다.The additive having the structure of Formula 1 has a bicyclic carbonate ester structure.

이차전지용 전해액 첨가제Electrolyte additive for secondary battery

본 발명의 이차전지용 전해액은 비수계 용매; 리튬염; 및 상기 화학식 1의 구조를 갖는 첨가제;를 포함한다.The electrolyte for a secondary battery of the present invention includes a non-aqueous solvent; Lithium salt; And an additive having the structure of Formula 1 above.

상기 비수계 용매는 이차전지용 전해액에 포함되는 리튬염 및 첨가제에 대한 용해도가 높은 것이 바람직하며, 예컨대, 디메틸 카보네이트(dimethyl carbonate), 디에틸 카보네이트(diethyl carbonate), 에틸메틸 카보네이트(ethylmethyl carbonate), 디프로필 카보네이트(dipropyl carbonate), 메틸프로필 카보네이트(methylpropyl carbonate), 에틸프로필 카보네이트(ethylpropyl carbonate), 에틸렌 카보네이트(ethylene carbonate), 프로필렌 카보네이트(propylene carbonate), 부틸렌 카보네이트(butylene carbonate) 및 감마부티로락톤(gamma-butyrolactone)으로 이루어진 군으로부터 선택된 1종 이상일 수 있다. 구체적으로, 상기 비수계 용매는 디메틸 카보네이트, 디에틸 카보네이트, 에틸메틸 카보네이트, 디프로필 카보네이트, 메틸프로필 카보네이트 및 에틸프로필 카보네이트로 이루어진 군으로부터 선택된 1종 이상의 선형 카보네이트계 용매, 및 에틸렌 카보네이트, 프로필렌 카보네이트, 부틸렌 카보네이트 및 감마부티로락톤으로 이루어진 군으로부터 선택된 1종 이상의 환형 카보네이트계 용매를 포함할 수 있다. The non-aqueous solvent is preferably high in solubility in lithium salts and additives contained in the electrolyte for secondary batteries, for example, dimethyl carbonate, diethyl carbonate, ethylmethyl carbonate, di Dipropyl carbonate, methylpropyl carbonate, ethylpropyl carbonate, ethylene carbonate, propylene carbonate, butylene carbonate and gamma butyrolactone ( gamma-butyrolactone) may be one or more selected from the group consisting of. Specifically, the non-aqueous solvent is at least one linear carbonate-based solvent selected from the group consisting of dimethyl carbonate, diethyl carbonate, ethylmethyl carbonate, dipropyl carbonate, methylpropyl carbonate and ethylpropyl carbonate, and ethylene carbonate, propylene carbonate, It may include at least one cyclic carbonate-based solvent selected from the group consisting of butylene carbonate and gamma butyrolactone.

상기 비수계 용매는 탈수된 것을 사용하는 것이 바람직하며, 비수계 용매 중 수분의 농도는 150 중량ppm 이하일 수 있다. 비수계 용매의 수분농도가 상기 범위 내일 경우, 전해질 내 리튬염이 분해되어 전해액 성능의 최적화를 이루기 어려운 문제 및 상기 화학식 1의 구조를 갖는 첨가제가 가수분해되는 문제를 방지할 수 있다.It is preferable to use a dehydrated non-aqueous solvent, and the concentration of moisture in the non-aqueous solvent may be 150 ppm by weight or less. When the moisture concentration of the non-aqueous solvent is within the above range, it is possible to prevent a problem in which it is difficult to optimize the electrolyte performance due to decomposition of a lithium salt in the electrolyte and a problem in which the additive having the structure of Formula 1 is hydrolyzed.

상기 리튬염은 전해액의 이온 전도성을 향상시키는 역할을 한다. 구체적으로, 상기 리튬염은 LiClO4, LiSO3CF3, LiPF6, LiBF4, LiAsF6, LiN(SO2CF3)2, LiN(SO2C2F5)2, LiN(SO2F)2 및 LiB(C2O4)2로 이루어진 군으로부터 선택된 1종 이상을 포함할 수 있다.The lithium salt serves to improve the ionic conductivity of the electrolyte. Specifically, the lithium salt is LiClO 4 , LiSO 3 CF 3 , LiPF 6 , LiBF 4 , LiAsF 6 , LiN(SO 2 CF 3 ) 2 , LiN(SO 2 C 2 F 5 ) 2 , LiN(SO 2 F) 2 and LiB(C 2 O 4 ) 2 It may include at least one selected from the group consisting of.

상기 전해액은 상기 비수계 용매 1 리터를 기준으로 0.9 내지 3.0 몰의 리튬염을 포함할 수 있다. 구체적으로, 상기 전해액은 상기 비수계 용매 1 리터를 기준으로 1.0 내지 2.0 몰의 리튬염을 포함할 수 있다. 상기 함량 범위로 리튬염을 포함할 경우, 전해액의 적절한 이온 전도성을 확보할 수 있고, 리튬염 함량 대비 이온 전도성 상승효과가 최적을 유지하여 경제적이다.The electrolyte may contain 0.9 to 3.0 moles of lithium salt based on 1 liter of the non-aqueous solvent. Specifically, the electrolyte may contain 1.0 to 2.0 moles of lithium salt based on 1 liter of the non-aqueous solvent. When a lithium salt is included in the above content range, an appropriate ion conductivity of the electrolyte can be secured, and an effect of synergizing ion conductivity relative to the lithium salt content is maintained optimally, which is economical.

상기 이차전지용 전해액은 상기 화학식 1의 구조를 갖는 첨가제를 전해액 총 중량을 기준으로 0.1 내지 10 중량%의 함량으로 포함할 수 있다. 구체적으로, 상기 전해액은 상기 화학식 1의 구조를 갖는 첨가제를 전해액 총 중량을 기준으로 0.1 내지 8 중량%, 0.1 내지 6 중량%, 0.1 내지 4 중량%, 0.1 내지 3 중량%, 0.2 내지 5.0 중량%, 0.5 내지 10 중량%, 0.5 내지 8 중량%, 0.5 내지 6 중량%, 0.5 내지 4 중량%, 3 내지 10 중량%, 3 내지 8 중량% 또는 3 내지 6 중량%의 함량으로 포함할 수 있다. 상기 함량 범위로 첨가제를 포함할 경우, 전지의 저항감소를 통한 출력개선 효과가 충분하고, 전해액에 대한 첨가제의 용해도가 감소하여 화학적 저장 안정성을 떨어뜨리는 문제를 방지할 수 있다.The electrolyte for a secondary battery may include an additive having the structure of Formula 1 in an amount of 0.1 to 10% by weight based on the total weight of the electrolyte. Specifically, the electrolyte is 0.1 to 8% by weight, 0.1 to 6% by weight, 0.1 to 4% by weight, 0.1 to 3% by weight, 0.2 to 5.0% by weight based on the total weight of the electrolyte. , 0.5 to 10% by weight, 0.5 to 8% by weight, 0.5 to 6% by weight, 0.5 to 4% by weight, 3 to 10% by weight, 3 to 8% by weight, or 3 to 6% by weight. When the additive is included in the above content range, the effect of improving the output by reducing the resistance of the battery is sufficient, and the solubility of the additive in the electrolyte is reduced, thereby preventing the problem of deteriorating the chemical storage stability.

또한, 상기 이차전지용 전해액은 상기 화학식 1의 구조를 갖는 첨가제 이외에 공지된 이차전지용 전해액 첨가제를 포함할 수 있다. 상기 공지된 이차전지용 전해액 첨가제는, 예를 들어, 비닐렌 카보네이트(vinylene carbonate), 플루오로에틸렌 카보네이트 (fluoroethylene carbonate), 숙시노니트릴(succinonitrile), 아디포니트릴(adiponitrile), 비닐 에틸렌 카보네이트(vinyl ethylene carbonate), 리튬 디플루오로 비스옥살라토 포스페이트(lithium difluoro bisoxalato phosphate), 리튬 테트라플루오로옥살라토 포스페이트(lithium tetrafluorooxalato phosphate), 리튬 디플루오로옥살라토 보레이트(lithium difluorooxalto borate), 리튬 비스옥살라토 보레이트(lithium bisoxalto borate), 리튬 디플루오로 포스페이트(lithium difluoro phosphate), 프로펜 설톤(propene sultone), 프로판 설톤(propane sultone), 에틸렌 설페이트(ethylene sulfate) 및 에틸렌 설파이트(ethylene sulfite)를 들 수 있다. In addition, the electrolyte for a secondary battery may include a known additive for an electrolyte for a secondary battery in addition to the additive having the structure of Formula 1 above. The known electrolyte solution additives for secondary batteries are, for example, vinylene carbonate, fluoroethylene carbonate, succinonitrile, adiponitrile, vinyl ethylene carbonate. carbonate), lithium difluoro bisoxalato phosphate, lithium tetrafluorooxalato phosphate, lithium difluorooxalto borate, lithium bisjade Salato borate (lithium bisoxalto borate), lithium difluoro phosphate (lithium difluoro phosphate), propene sultone (propene sultone), propane sultone (propane sultone), ethylene sulfate (ethylene sulfate) and ethylene sulfite (ethylene sulfite) Can be lifted.

상기 공지된 이차전지용 전해액 첨가제는 상기 전해액의 성능 저하 및 상기 화학식 1의 구조를 갖는 첨가제의 효과에 영향을 주지 않는 함량 범위로 첨가될 수 있다. 예를 들어, 전해액 총 중량을 기준으로 0.1 중량% 이상, 또는 0.1 내지 10 중량%의 함량으로 첨가될 수 있다.The known electrolyte solution additive for a secondary battery may be added in a content range that does not affect the performance of the electrolyte solution and the effect of the additive having the structure of Formula 1 above. For example, it may be added in an amount of 0.1% by weight or more, or 0.1 to 10% by weight based on the total weight of the electrolyte.

상기 이차전지용 전해액은 비수계 용매, 리튬염 및 상기 화학식 1의 구조를 갖는 첨가제를 혼합하고 교반함으로써 제조될 수 있으며, 이때 전해액에 통상적으로 사용되는 공지의 전해액 첨가제가 더 혼합될 수 있다.The electrolyte for a secondary battery may be prepared by mixing and stirring a non-aqueous solvent, a lithium salt, and an additive having the structure of Formula 1, and at this time, a known electrolyte additive commonly used in the electrolyte may be further mixed.

이차전지Secondary battery

본 발명의 이차전지는 상술한 바와 같은 이차전지용 전해액을 포함한다. 구체적으로, 상기 이차전지는 상술한 바와 같은 이차전지용 전해액을 양극, 음극 및 그 사이에 분리막을 포함하는 전극 조립체에 주입하여 제조된 것일 수 있다. The secondary battery of the present invention includes the electrolyte for a secondary battery as described above. Specifically, the secondary battery may be manufactured by injecting the electrolyte for a secondary battery as described above into an electrode assembly including a positive electrode, a negative electrode, and a separator therebetween.

상기 이차전지는 그 종류를 특별히 한정하지 않으며, 예를 들어, 리튬이온 전지, 리튬이온 폴리머 전지, 또는 리튬 폴리머 전지일 수 있다.The type of the secondary battery is not particularly limited, and may be, for example, a lithium ion battery, a lithium ion polymer battery, or a lithium polymer battery.

이하, 구체적인 실시예 및 비교예를 통하여 본 발명을 더욱 상세히 설명한다. 하기 실시예는 본 발명을 보다 구체적으로 설명하기 위한 것으로서, 본 발명이 하기 실시예에 의해 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail through specific examples and comparative examples. The following examples are intended to illustrate the present invention in more detail, and the present invention is not limited by the following examples.

[[ 실시예Example ]]

제조예Manufacturing example 1. 첨가제의 제조 1. Preparation of additives

50 ℃의 오일 배쓰에 1,000 ㎖의 3구 플라스크와 컨덴서를 설치하였다. 상기 3구 플라스크에 110 g의 1,1,2,2-테트라클로로에탄을 넣고 온도를 안정화시킨 후, 180 g의 농축 황산(농도: 98 %)과 2 g의 황산아연(ZnSO4)을 넣었다. 이후 326 g의 삼산화황(SO3)을 천천히 주입하며 반응을 개시하였으며, 반응액은 초기에 투명하였으며 반응이 진행되며 점점 연한 갈색의 점성을 갖는 용액으로 변했다. 12 시간 반응 후 반응물을 황산으로 세척하고, 50 g의 물과 300 g의 디메틸카보네이트(dimethylcarbonate)를 첨가한 후 18 시간 동안 교반하였다. 이후 고체의 추가 생성이 없을 때 반응을 종결시켰다.A 1,000 ml three-necked flask and a condenser were installed in an oil bath at 50°C. 110 g of 1,1,2,2-tetrachloroethane was added to the three-necked flask and the temperature was stabilized, and then 180 g of concentrated sulfuric acid (concentration: 98%) and 2 g of zinc sulfate (ZnSO 4 ) were added. . Then, 326 g of sulfur trioxide (SO 3 ) was slowly injected to initiate the reaction, and the reaction solution was initially transparent and the reaction proceeded, gradually changing to a light brown viscous solution. After the reaction for 12 hours, the reaction product was washed with sulfuric acid, 50 g of water and 300 g of dimethylcarbonate were added, followed by stirring for 18 hours. The reaction was then terminated when there was no further formation of solids.

반응액을 여과기로 고액 분리한 후, 고체를 상온 및 20 torr 하의 조건에서 24 시간 동안 진공 건조하여 하기 화학식 1의 구조를 갖는 바이사이클로 글리옥살 카보네이트(bicyclo glyoxal carbonate) 53.6 g을 수득하였다(수율 : 57 %).After solid-liquid separation of the reaction solution with a filter, the solid was vacuum-dried at room temperature and under 20 torr for 24 hours to obtain 53.6 g of bicyclo glyoxal carbonate having the structure of the following formula (1) (yield: 57%).

[화학식 1][Formula 1]

Figure 112017039529448-pat00004
Figure 112017039529448-pat00004

실험예Experimental example 1. One.

제조예 1에서 제조한 바이사이클로 글리옥살 카보네이트는 핵자기공명스펙트럼(NMR)(600 ㎒ FT-NMR Spectrometer(JEOL OXFORD 600))을 사용하여 상기 실시예 1의 바이사이클로 글리옥살 카보네이트의 1H-NMR 및 13C-NMR 스펙트럼을 얻었다. The bicyclo glyoxal carbonate prepared in Preparation Example 1 was 1 H-NMR of the bicyclo glyoxal carbonate of Example 1 using a nuclear magnetic resonance spectrum (NMR) (600 MHz FT-NMR Spectrometer (JEOL OXFORD 600)). And a 13 C-NMR spectrum was obtained.

- 1H-NMR (500 ㎒, CD3CN): δ 7.1ppm (s, 2H) -1 H-NMR (500 ㎒, CD 3 CN): δ 7.1ppm (s, 2H)

- 13C-NMR (500 ㎒, CD3CN): δ 102.2ppm (s, 2C) -13 C-NMR (500 ㎒, CD 3 CN): δ 102.2ppm (s, 2C)

실시예Example 1. 전해액의 제조 1. Preparation of electrolyte

에틸렌 카보네이트 43 g, 에틸메틸 카보네이트 59 g 및 디에틸 카보네이트 38 g을 혼합하여 혼합액을 제조하고, 상기 혼합액에 16.7 g의 LiPF6를 투입하여 1.1 몰/ℓ의 농도의 LiPF6 용액을 제조하였다. 이후, 전해액 총 중량을 기준으로 0.5 중량%의 상기 제조예 1의 바이사이클로 글리옥살 카보네이트를 첨가하고 혼합하여, 이차전지용 전해액을 제조하였다.A mixture was prepared by mixing 43 g of ethylene carbonate, 59 g of ethylmethyl carbonate, and 38 g of diethyl carbonate, and 16.7 g of LiPF 6 was added to the mixture to prepare a LiPF 6 solution having a concentration of 1.1 mol/L. Thereafter, 0.5% by weight of the bicyclo glyoxal carbonate of Preparation Example 1 was added and mixed, based on the total weight of the electrolyte, to prepare an electrolyte for a secondary battery.

실시예Example 2 내지 6 및 2 to 6 and 비교예Comparative example 1 내지 4. 1 to 4.

하기 표 1에 기재된 바와 같이, 첨가제의 함량 및 종류를 변화시킨 것을 제외하고는, 실시예 1과 동일한 방법으로 이차전지용 전해액을 제조하였다.As shown in Table 1 below, an electrolyte solution for a secondary battery was prepared in the same manner as in Example 1, except that the content and type of additives were changed.

첨가제의 종류Type of additive 첨가제의 함량Content of additives 실시예 1Example 1 바이사이클로 글리옥살 카보네이트Bicycloglyoxal carbonate 0.5 중량%0.5% by weight 실시예 2Example 2 바이사이클로 글리옥살 카보네이트Bicycloglyoxal carbonate 3.0 중량%3.0% by weight 실시예 3Example 3 바이사이클로 글리옥살 카보네이트Bicycloglyoxal carbonate 4.0 중량%4.0% by weight 실시예 4Example 4 바이사이클로 글리옥살 카보네이트Bicycloglyoxal carbonate 6.0 중량%6.0% by weight 실시예 5Example 5 바이사이클로 글리옥살 카보네이트Bicycloglyoxal carbonate 8.0 중량%8.0% by weight 실시예 6Example 6 바이사이클로 글리옥살 카보네이트Bicycloglyoxal carbonate 0.04 중량%0.04% by weight 비교예 1Comparative Example 1 1,3-프로판 설톤(입수처: Aldrich)1,3-propane sultone (import: Aldrich) 0.2 중량%0.2% by weight 비교예 2Comparative Example 2 1,3-프로판 설톤(입수처: Aldrich)1,3-propane sultone (import: Aldrich) 3.0 중량%3.0% by weight 비교예 3Comparative Example 3 리튬 비스(옥살라토) 붕산염
(입수처: Chemetall)Lithium bis (oxalato) borate
(Imported from: Chemetall) 5.0 중량%5.0% by weight 비교예 4Comparative Example 4 1,3-프로펜 설톤(입수처 : TCI)1,3-propene sultone (importer: TCI) 5.0 중량%5.0% by weight

실험예Experimental example 2. 고온/고전압 환경하에서 리튬 이차전지의 임피던스( 2. Impedance of lithium secondary battery in high temperature/high voltage environment ( mΩmΩ ) 측정) Measure

양극 활물질인 LiNi5Co2Mn3과 LiMnO2을 1:1 중량비로 혼합한 양극재, 및 음극 활물질로 인조흑연을 사용한 음극재를 사용하여 통상의 방법으로 1.3 Ah 파우치 전지를 조립하고, 상기 실시예 1 내지 6 및 비교예 1 내지 4의 이차전지용 전해액을 각각 6 g씩 주입하여 이차전지를 완성하였다. 전지 화성 공정을 수행한 후, 25 ℃에서 1.3 Ah 파우치 전지의 만충전 대비 60 %의 충전상태 전압을 유지한 채 3 C(쿨롱)로 10 초간 방전시켰을 때 얻어지는 임피던스를 PNE-0506 충방전기(제조사: (주)PNE 솔루션)로 측정하여 하기 표 2에 나타내었다.A 1.3 Ah pouch battery was assembled by a conventional method using a positive electrode material in which a positive electrode active material LiNi 5 Co 2 Mn 3 and LiMnO 2 were mixed in a 1:1 weight ratio, and a negative electrode material using artificial graphite as the negative electrode active material, Secondary batteries were completed by injecting 6 g each of the electrolyte solutions for secondary batteries of Examples 1 to 6 and Comparative Examples 1 to 4. After performing the battery formation process, the impedance obtained when discharging at 3 C (Coulomb) for 10 seconds while maintaining a charged state voltage of 60% compared to the full charge of a 1.3 Ah pouch battery at 25 °C was determined by the PNE-0506 charger (manufacturer). : Measured by PNE Solution Co., Ltd.) and shown in Table 2 below.

또한, 동일 전지를 만충전 상태에서, 충방전기(상기와 동일한 장비 사용)로 임피던스를 측정한 후, 60 ℃ 고온 오븐에 10 일 또는 20 일 동안 보관 후 각각의 방전 임피던스를 상술한 바와 동일한 방법으로 측정하여 표 2에 나타내었다.In addition, the same battery is fully charged, the impedance is measured with a charger (using the same equipment as above), and then stored in a high-temperature oven at 60° C. for 10 or 20 days, and then each discharge impedance is determined in the same manner as described above. It was measured and shown in Table 2.

임피던스 (mΩ)Impedance (mΩ) 25 ℃ (초기)25 ℃ (initial) 60 ℃ 보관 10일 후After 10 days of storage at 60 ℃ 60 ℃ 보관 20일 후After 20 days of storage at 60 ℃ 실시예 1Example 1 3737 3939 5353 실시예 2Example 2 3535 4545 5252 실시예 3Example 3 3333 4343 5151 실시예 4Example 4 3535 4343 5050 실시예 5Example 5 3131 4747 5454 실시예 6Example 6 3636 5858 7373 비교예 1Comparative Example 1 3232 7171 101101 비교예 2Comparative Example 2 3636 6969 8686 비교예 3Comparative Example 3 5252 5757 6161 비교예 4Comparative Example 4 5050 5252 5555

상기 표 2에서 보는 바와 같이, 실시예 1 내지 5의 이차전지용 전해액을 사용한 전지는, 비교예 1 내지 4의 전해액을 사용한 전지와 비교하여, 방전시 임피던스가 소폭으로 증가되었다. 이는 본 발명의 첨가제(상기 화학식 1의 구조를 찾는 첨가제)가 전지의 방전시 전극과 전해질 계면 사이의 저항을 낮춰 전지의 출력 특성이 향상됨을 보여주는 결과이다.As shown in Table 2, the batteries using the electrolyte solutions for secondary batteries of Examples 1 to 5 showed a slight increase in impedance during discharge compared to the batteries using the electrolyte solutions of Comparative Examples 1 to 4. This is a result showing that the additive of the present invention (the additive for finding the structure of Formula 1) lowers the resistance between the electrode and the electrolyte interface when the battery is discharged, thereby improving the output characteristics of the battery.

한편, 첨가제로 리튬 비스(옥살레이트) 붕산염 또는 1,3-프로펜 설톤을 사용한 비교예 3 및 4의 전해액을 사용한 전지는, 본 발명의 첨가제를 포함하는 실시예 1 내지 5와 비교하여, 상온에서 초기 임피던스가 현저히 높았다.On the other hand, the battery using the electrolyte solutions of Comparative Examples 3 and 4 using lithium bis(oxalate) borate or 1,3-propene sultone as an additive, compared with Examples 1 to 5 containing the additive of the present invention, at room temperature The initial impedance was remarkably high at.

실험예Experimental example 3. 리튬 이차전지의 저온 환경하에서의 저장특성 ( 3. Storage characteristics of lithium secondary battery under low temperature environment ( 용량회복성Capacity recovery , , %% ))

상기 실험예 2와 동일한 방법으로 전지 화성공정을 수행하여 이차전지(1.3 Ah 파우치 전지)를 얻은 후, 1.3 Ah 파우치 전지를 만충전 상태로 -10 ℃ 챔버에 10 시간 동안 방지한 후 0.5 C의 속도 및 2.7 V로 방전한 후 0.5 C의 속도 및 4.2 V로 충전하는 충전하는 것을 1 사이클로, 15 사이클 후 초기 충전량 대비 방전용량을 PNE-0506 충방전기(제조사: (주)PNE 솔루션)로 측정하여 하기 표 3에 나타내었다.After performing the battery formation process in the same manner as in Experimental Example 2 to obtain a secondary battery (1.3 Ah pouch battery), the 1.3 Ah pouch battery was prevented in a -10°C chamber for 10 hours in a fully charged state, followed by a rate of 0.5 C. And charging at a rate of 0.5 C and 4.2 V after discharging at 2.7 V as 1 cycle, and after 15 cycles, the discharge capacity compared to the initial charge amount was measured with a PNE-0506 charger (manufacturer: PNE Solution Co., Ltd.) It is shown in Table 3.

저온 사이클에서의 상대적인 방전량 (%)Relative discharge amount in low temperature cycle (%) 초기 (%)Early (%) 15회째 방전량 (초기대비%)Discharge amount of the 15th time (% compared to the initial period) 실시예 1Example 1 100100 5959 실시예 2Example 2 100100 6161 실시예 3Example 3 100100 6666 실시예 4Example 4 100100 6262 실시예 5Example 5 100100 6565 실시예 6Example 6 100100 5555 비교예 1Comparative Example 1 100100 5252 비교예 2Comparative Example 2 100100 4444 비교예 3Comparative Example 3 100100 5151 비교예 4Comparative Example 4 100100 3535

상기 표 3에서 보는 바와 같이, 실시예 1 내지 5의 전해액을 사용한 전지는, 비교예 1 내지 4의 전해액을 사용한 전지와 비교하여, 전지 초기 방전량 대비 15 회째 방전량의 저하가 적었다. 이는 본 발명의 첨가제가 저온에서 전지의 충·방전 중 발생하는 전기화학적 전극반응속도의 감소 또는 전해액의 이온전도도의 급격한 저하는 방지함을 보여주는 결과이다. 이로써 본 발명의 첨가제를 포함하는 전지가 저온에서도 안정적인 충방전 용량을 구현할 수 있음을 확인할 수 있다.As shown in Table 3, the batteries using the electrolyte solutions of Examples 1 to 5 showed less decrease in the discharge amount at the 15th time compared to the initial discharge amount of the battery compared to the batteries using the electrolyte solutions of Comparative Examples 1 to 4. This is a result showing that the additive of the present invention prevents a decrease in the electrochemical electrode reaction rate or a rapid decrease in the ionic conductivity of the electrolyte that occurs during charging and discharging of a battery at low temperatures. As a result, it can be seen that the battery including the additive of the present invention can achieve stable charging and discharging capacity even at low temperatures.

Claims (8)

하기 화학식 1의 구조를 갖는 이차전지용 전해액 첨가제:
[화학식 1]
Figure 112017039529448-pat00005
.
An electrolyte solution additive for a secondary battery having the structure of the following formula (1):
[Formula 1]
Figure 112017039529448-pat00005
.
 비수계 용매;
리튬염; 및
하기 화학식 1의 구조를 갖는 첨가제;를 포함하는, 이차전지용 전해액:
[화학식 1]
Figure 112017039529448-pat00006
.
Non-aqueous solvent;
Lithium salt; And
An electrolyte solution for a secondary battery containing;
[Formula 1]
Figure 112017039529448-pat00006
.
 제2항에 있어서,
상기 화학식 1의 구조를 갖는 첨가제를 전해액 총 중량을 기준으로 0.1 내지 10 중량%의 함량으로 포함하는, 이차전지용 전해액.
The method of claim 2,
An electrolyte solution for a secondary battery comprising the additive having the structure of Formula 1 in an amount of 0.1 to 10% by weight based on the total weight of the electrolyte.
 제2항에 있어서,
상기 비수계 용매가 디메틸 카보네이트(dimethyl carbonate), 디에틸 카보네이트(diethyl carbonate), 에틸메틸 카보네이트(ethylmethyl carbonate), 디프로필 카보네이트(dipropyl carbonate), 메틸프로필 카보네이트(methylpropyl carbonate), 에틸프로필 카보네이트(ethylpropyl carbonate), 에틸렌 카보네이트(ethylene carbonate), 프로필렌 카보네이트(propylene carbonate), 부틸렌 카보네이트(butylene carbonate) 및 감마-부티로락톤(gamma-butyrolactone)으로 이루어진 군으로부터 선택된 1종 이상인, 이차전지용 전해액.
The method of claim 2,
The non-aqueous solvent is dimethyl carbonate, diethyl carbonate, ethylmethyl carbonate, dipropyl carbonate, methylpropyl carbonate, ethylpropyl carbonate ), ethylene carbonate (ethylene carbonate), propylene carbonate (propylene carbonate), butylene carbonate (butylene carbonate) and gamma-butyrolactone (gamma-butyrolactone) at least one selected from the group consisting of, secondary battery electrolyte.
 제4항에 있어서,
상기 비수계 용매가
디메틸 카보네이트, 디에틸 카보네이트, 에틸메틸 카보네이트, 디프로필 카보네이트, 메틸프로필 카보네이트 및 에틸프로필 카보네이트로 이루어진 군으로부터 선택된 1종 이상의 선형 카보네이트계 용매, 및
에틸렌 카보네이트, 프로필렌 카보네이트, 부틸렌 카보네이트 및 감마-부티로락톤으로 이루어진 군으로부터 선택된 1종 이상의 환형 카보네이트계 용매를 포함하는, 이차전지용 전해액.
The method of claim 4,
The non-aqueous solvent is
At least one linear carbonate-based solvent selected from the group consisting of dimethyl carbonate, diethyl carbonate, ethylmethyl carbonate, dipropyl carbonate, methylpropyl carbonate and ethylpropyl carbonate, and
An electrolyte for a secondary battery comprising at least one cyclic carbonate-based solvent selected from the group consisting of ethylene carbonate, propylene carbonate, butylene carbonate and gamma-butyrolactone.
 제2항에 있어서,
상기 리튬염이 LiClO4, LiSO3CF3, LiPF6, LiBF4, LiAsF6, LiN(SO2CF3)2, LiN(SO2C2F5)2, LiN(SO2F)2 및 LiB(C2O4)2로 이루어진 군으로부터 선택된 1종 이상을 포함하는, 이차전지용 전해액.
The method of claim 2,
The lithium salt is LiClO 4 , LiSO 3 CF 3 , LiPF 6 , LiBF 4 , LiAsF 6 , LiN(SO 2 CF 3 ) 2 , LiN(SO 2 C 2 F 5 ) 2 , LiN(SO 2 F) 2 and LiB (C 2 O 4 ) A secondary battery electrolyte containing at least one selected from the group consisting of 2.
제2항에 있어서,
상기 전해액이 상기 비수계 용매 1 리터를 기준으로 0.9 내지 3.0 몰의 리튬염을 포함하는, 이차전지용 전해액.
The method of claim 2,
The electrolyte solution for a secondary battery containing 0.9 to 3.0 moles of lithium salt based on 1 liter of the non-aqueous solvent.
 제2항 내지 제7항 중 어느 한 항의 이차전지용 전해액을 포함하는, 이차전지.A secondary battery comprising the electrolyte for a secondary battery according to any one of claims 2 to 7.
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