KR102555960B1 - Electrolytic solution additive for electrochemical device and electrolytic solution containing the same - Google Patents
Electrolytic solution additive for electrochemical device and electrolytic solution containing the same Download PDFInfo
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- KR102555960B1 KR102555960B1 KR1020210059169A KR20210059169A KR102555960B1 KR 102555960 B1 KR102555960 B1 KR 102555960B1 KR 1020210059169 A KR1020210059169 A KR 1020210059169A KR 20210059169 A KR20210059169 A KR 20210059169A KR 102555960 B1 KR102555960 B1 KR 102555960B1
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- 239000008151 electrolyte solution Substances 0.000 title claims abstract description 37
- 239000000654 additive Substances 0.000 title claims abstract description 33
- 230000000996 additive effect Effects 0.000 title claims abstract description 31
- 239000003792 electrolyte Substances 0.000 claims abstract description 22
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 claims abstract description 18
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 14
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims abstract description 5
- -1 spirobipyrrolidinium tetrafluoroborate Chemical compound 0.000 claims description 9
- 229940021013 electrolyte solution Drugs 0.000 description 31
- 239000003990 capacitor Substances 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 15
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 230000003247 decreasing effect Effects 0.000 description 4
- 230000006872 improvement Effects 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 2
- 229910013063 LiBF 4 Inorganic materials 0.000 description 2
- 229910013684 LiClO 4 Inorganic materials 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- LRESCJAINPKJTO-UHFFFAOYSA-N bis(trifluoromethylsulfonyl)azanide;1-ethyl-3-methylimidazol-3-ium Chemical compound CCN1C=C[N+](C)=C1.FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F LRESCJAINPKJTO-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- CXYAFFSHJZNAKZ-UHFFFAOYSA-N C[Si]1(O[Si](O[Si](O[Si](O1)(C)C)(C)C)(C)C)C.C[Si]1(O[Si](O[Si](O[Si](O1)(C)C)(C)C)(C)C)C Chemical compound C[Si]1(O[Si](O[Si](O[Si](O1)(C)C)(C)C)(C)C)C.C[Si]1(O[Si](O[Si](O[Si](O1)(C)C)(C)C)(C)C)C CXYAFFSHJZNAKZ-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910016978 MnOx Inorganic materials 0.000 description 1
- 229910003307 Ni-Cd Inorganic materials 0.000 description 1
- 229910018095 Ni-MH Inorganic materials 0.000 description 1
- 229910018477 Ni—MH Inorganic materials 0.000 description 1
- 229910019897 RuOx Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003985 ceramic capacitor Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- VRIVJOXICYMTAG-IYEMJOQQSA-L iron(ii) gluconate Chemical compound [Fe+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O VRIVJOXICYMTAG-IYEMJOQQSA-L 0.000 description 1
- 235000015110 jellies Nutrition 0.000 description 1
- 239000008274 jelly Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
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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
- H01G11/62—Liquid electrolytes characterised by the solute, e.g. salts, anions or cations therein
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- General Chemical & Material Sciences (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
본 발명은 전기화학소자의 작동 온도를 확장할 수 있는 전기화학소자용 전해액 첨가제 및 그를 포함하는 전해액에 관한 것이다. 본 발명에 따른 전기화학소자용 전해액은 전해질, SL(Sulfolane)과 AN(acetonitrile)이 혼합된 용매, 및 옥타메틸사이클로테트라실록산(octamethylcyclotetrasiloxane)의 첨가제를 포함한다.The present invention relates to an electrolyte solution additive for an electrochemical device capable of extending the operating temperature of the electrochemical device and an electrolyte solution including the same. The electrolyte solution for an electrochemical device according to the present invention includes an electrolyte, a solvent in which SL (Sulfolane) and AN (acetonitrile) are mixed, and an octamethylcyclotetrasiloxane additive.
Description
본 발명은 전기화학소자용 전해액에 관한 것으로, 더욱 상세하게는 전기화학소자의 작동 온도를 확장할 수 있는 전기화학소자용 전해액 첨가제 및 그를 포함하는 전해액에 관한 것이다.The present invention relates to an electrolyte solution for an electrochemical device, and more particularly, to an electrolyte solution additive for an electrochemical device capable of extending the operating temperature of an electrochemical device and an electrolyte solution containing the same.
정보화 시대에는 각종 정보통신기기를 통해 다양하고 유용한 정보를 실시간으로 수집 및 활용하는 고부가가치 산업이 주도하고 있으며, 이러한 시스템의 신뢰성 확보를 위해서는 안정적인 에너지의 공급이 중요한 요소로 인식되고 있다.In the information age, high value-added industries that collect and utilize various useful information in real time through various information and communication devices are leading, and stable energy supply is recognized as an important factor to secure the reliability of these systems.
안정적인 에너지 확보의 일환으로서, 전기에너지를 화학에너지로 변환하여 저장하였다가 필요시 다시 전기에너지로 변환하여 쓸 수 있는 전기화학소자(electrochemical device)가 사용되고 있다.As part of securing stable energy, an electrochemical device that converts electrical energy into chemical energy, stores it, and then converts it into electrical energy when necessary is used.
이러한 전기화학소자로는 Ni-MH 전지, Ni-Cd 전지, 납축전지 및 리튬이차전지와 같은 이차전지와, 높은 출력 밀도를 가지면서 충방전 수명이 무제한에 가까운 슈퍼 커패시터, 알루미늄 전해 커패시터 및 세라믹 커패시터 등이 있다.These electrochemical devices include secondary batteries such as Ni-MH batteries, Ni-Cd batteries, lead-acid batteries and lithium secondary batteries, supercapacitors with high power density and almost unlimited charge and discharge life, aluminum electrolytic capacitors, and ceramic capacitors. etc.
특히 슈퍼 커패시터는 전기이중층 커패시터(EDLC; Electric Double Layer Capacitor), 유사 커패시터(pseudo capacitor), 리튬 이온 커패시터(LIC; lithium ion capacitor)와 같은 하이브리드 커패시터(hybrid capacitor) 등이 있으며, 그 형태에 따라 파우치형, 캔형 등이 있다. 캔형은 원통형(권취형), 각형 등을 포함한다. 이때, 원통형은 셀을 젤리롤 형태로 와인딩(winding)한 다음, 원통형 케이스에 내장하여 제작하고 있다.In particular, supercapacitors include electric double layer capacitors (EDLC), pseudo capacitors, and hybrid capacitors such as lithium ion capacitors (LIC). There are molds, cans, etc. The can shape includes a cylindrical shape (wound shape), a prismatic shape, and the like. At this time, the cylindrical shape is manufactured by winding the cell into a jelly roll shape and then inserting it into a cylindrical case.
여기서 전기이중층 커패시터는 서로 다른 상의 계면에 형성된 전기이중층에서 발생하는 정전하현상을 이용한 커패시터로서, 에너지 저장 메커니즘이 산화 및 환원과정에 의존하는 배터리에 비하여 충방전 속도가 빠르고 충방전 효율이 높으며 사이클 특성이 월등하여 백업 전원에 광범위하게 사용되며, 향후 전기자동차의 보조전원으로서의 가능성도 무한하다.Here, the electric double layer capacitor is a capacitor using the electrostatic charge phenomenon generated in the electric double layer formed at the interface of different phases. Compared to batteries whose energy storage mechanism depends on oxidation and reduction processes, the electric double layer capacitor has faster charging and discharging speed, higher charge and discharge efficiency, and cycle characteristics. It is widely used for backup power, and the possibility as an auxiliary power source for electric vehicles in the future is infinite.
유사 커패시터는 는 전극과 전기화학 산화물 반응물의 산화-환원 반응을 이용하여 화학 반응을 전기적 에너지로 전환하여 저장하는 커패시터이다. 유사 커패시터는 전기이중층 커패시터가 전기화학 이중층형 전극 표면에 형성된 이중층에만 전하를 저장하는 데 비하여 전극 재료의 표면 근처까지 전하를 저장 할 수 있어 저장 용량이 전기이중층 커패시터에 비하여 약 5배 정도 크다. 금속산화물 전극재료로는 RuOx, IrOx, MnOx 등이 사용되고 있다.A pseudocapacitor is a capacitor that converts a chemical reaction into electrical energy and stores it using an oxidation-reduction reaction between an electrode and an electrochemical oxide reactant. Compared to electric double layer capacitors that store charges only in the double layer formed on the surface of the electrochemical double layer electrode, the pseudocapacitor can store charges up to the surface of the electrode material, so the storage capacity is about 5 times greater than that of electric double layer capacitors. RuOx, IrOx, MnOx, etc. are used as metal oxide electrode materials.
그리고 리튬 이온 커패시터는 기존 전기이중층 커패시터의 고출력 및 장수명 특성과, 리튬 이온 전지의 고에너지밀도를 결합한 새로운 개념의 이차전지 시스템이다. 전기이중층 내 전하의 물리적 흡착반응을 이용하는 전기이중층 커패시터는 우수한 출력특성 및 수명특성에도 불구하고 낮은 에너지밀도 때문에 다양한 응용분야에 적용이 제한되고 있다. 이러한 전기이중층 커패시터의 문제점을 해결하는 수단으로서 음극 활물질로서 리튬 이온을 삽입 및 탈리할 수 있는 탄소계 소재를 이용하는 리튬 이온 커패시터가 제안되었으며, 리튬 이온 커패시터는 이온화 경향이 큰 리튬 이온을 음극에 미리 도핑하여 음극의 전위를 대폭적으로 낮출 수 있고, 셀 전압도 종래의 전기이중층 커패시터의 2.5 V 대비 크게 향상된 3.8 V 이상의 고전압 구현이 가능하며 높은 에너지 밀도를 발현할 수 있다.The lithium ion capacitor is a secondary battery system of a new concept that combines the high power and long life characteristics of conventional electric double layer capacitors with the high energy density of lithium ion batteries. Electric double-layer capacitors using the physical adsorption reaction of electric charges in the electric double-layer are limited in various application fields due to their low energy density despite their excellent output characteristics and lifespan characteristics. As a means to solve the problem of the electric double layer capacitor, a lithium ion capacitor using a carbon-based material capable of intercalating and deintercalating lithium ions as an anode active material has been proposed. Thus, the potential of the cathode can be drastically lowered, the cell voltage can be realized at a high voltage of 3.8 V or more, which is greatly improved compared to 2.5 V of the conventional electric double layer capacitor, and high energy density can be expressed.
하지만 슈퍼 커패시터를 포함한 전기화학소자는 고온에서 동작할 경우 전해질 분해 및 이온 불안정성이 발생하기 때문에, 전기화학소자는 작동 온도에 제한이 존재한다.However, since electrochemical decomposition and ion instability occur when an electrochemical device including a supercapacitor operates at a high temperature, the electrochemical device has a limitation in operating temperature.
이러한 문제점을 해소하기 위해서, 높은 이온전도성을 갖는 염이나 용매를 사용하거나 특성 개선을 위하여 전해액에 첨가제를 적용하는 등의 다양한 연구가 진행되고 있다.In order to solve these problems, various studies are being conducted, such as using salts or solvents having high ionic conductivity or applying additives to electrolytes to improve properties.
따라서 본 발명의 목적은 슈퍼 커패시터의 작동 온도를 확장할 수 있는 전기화학소자용 전해액 첨가제 및 그를 포함하는 전해액을 제공하는 데 있다.Accordingly, an object of the present invention is to provide an electrolyte solution additive for an electrochemical device capable of extending the operating temperature of a supercapacitor and an electrolyte solution including the same.
상기 목적을 달성하기 위하여, 본 발명은 전기화학소자용 전해액에 첨가되는 첨가제로서, 전해질, SL(Sulfolane) 및 AN(acetonitrile)을 포함하는 전해액에 첨가되는 옥타메틸사이클로테트라실록산(octamethylcyclotetrasiloxane)인 전기화학소자용 전해액 첨가제를 제공한다.In order to achieve the above object, the present invention is an additive added to an electrolyte solution for an electrochemical device, which is octamethylcyclotetrasiloxane added to an electrolyte solution containing an electrolyte, SL (Sulfolane) and AN (acetonitrile) Electrochemical An electrolyte solution additive for devices is provided.
상기 옥타메틸사이클로테트라실록산은 5 wt% 미만으로 첨가될 수 있다.The octamethylcyclotetrasiloxane may be added at less than 5 wt%.
상기 옥타메틸사이클로테트라실록산은 0.5 내지 1 wt%가 첨가될 수 있다.0.5 to 1 wt% of the octamethylcyclotetrasiloxane may be added.
본 발명은 또한, 전해질; SL(Sulfolane)과 AN(acetonitrile)이 혼합된 용매; 및 옥타메틸사이클로테트라실록산(octamethylcyclotetrasiloxane)의 첨가제;를 포함하는 전기화학소자용 전해액을 제공한다.The present invention also provides an electrolyte; A solvent in which SL (Sulfolane) and AN (acetonitrile) are mixed; And octamethylcyclotetrasiloxane (octamethylcyclotetrasiloxane) of the additive; provides an electrolyte solution for an electrochemical device containing.
상기 용매는 상기 SL 10 내지 50 wt%와, 상기 AN 50 내지 90 wt%를 포함할 수 있다.The solvent may include 10 to 50 wt% of the SL and 50 to 90 wt% of the AN.
그리고 상기 전해질은 SBPBF4(spirobipyrrolidinium tetrafluoroborate), TEABF4(tetraethylammonium tetrafluorborate), TEMABF4(triethylmethylammonium tetrafluorborate), EMIBF4(1-ethyl-3-methyl imidazolium tetrafluoborate), EMITFSI(1-ethyl-3-methyl imidazolium bis(trifluoromethane sulfonyl)imide), LiClO4, LiPF6, LiAsF6, 또는 LiBF4를 포함할 수 있다.And the electrolyte is SBPBF 4 (spirobipyrrolidinium tetrafluoroborate), TEABF 4 (tetraethylammonium tetrafluorborate), TEMABF 4 (triethylmethylammonium tetrafluorborate), EMIBF 4 (1-ethyl-3-methyl imidazolium tetrafluoroborate), EMITFSI (1-ethyl-3-methyl imidazolium bis (trifluoromethane sulfonyl)imide), LiClO 4 , LiPF 6 , LiAsF 6 , or LiBF 4 .
본 발명에 따르면, 전기화학소자용 전해액에 옥타메틸사이클로테트라실록산(octamethylcyclotetrasiloxane)을 첨가함으로써, 전기화학소자의 작동온도를 확장할 수 있다. 즉 옥타메틸사이클로테트라실록산이 첨가된 전해액에 대한 85℃ 및 85%RH에서의 고온고습 부하 테스트를 통해서, 옥타메틸사이클로테트라실록산이 첨가되지 않은 전해액과 대비하여, AC-ESR(equivalence series resistance; 등가직렬저항)이 감소하고 커패시턴스(capacitance)가 증가한 것을 확인할 수 있다. 고온고습 부하 테스트에서의 저항증가율과 용량감소율의 개선은 첨가제로 옥타메틸사이클로테트라실록산가 첨가된 전해액을 사용하는 전기화학소자의 작동온도가 확장되었음을 의미한다.According to the present invention, the operating temperature of the electrochemical device can be extended by adding octamethylcyclotetrasiloxane to the electrolyte solution for the electrochemical device. That is, through a high-temperature, high-humidity load test at 85 ° C and 85% RH for the electrolyte solution to which octamethylcyclotetrasiloxane was added, compared to the electrolyte solution to which octamethylcyclotetrasiloxane was not added, AC-ESR (equivalence series resistance; equivalent It can be seen that the series resistance) decreased and the capacitance increased. The improvement in the resistance increase rate and the capacity decrease rate in the high temperature and high humidity load test means that the operating temperature of the electrochemical device using the electrolyte with octamethylcyclotetrasiloxane added as an additive has been extended.
하기의 설명에서는 본 발명의 실시예를 이해하는데 필요한 부분만이 설명되며, 그 이외 부분의 설명은 본 발명의 요지를 벗어나지 않는 범위에서 생략될 것이라는 것을 유의하여야 한다.It should be noted that in the following description, only parts necessary for understanding the embodiments of the present invention are described, and descriptions of other parts will be omitted without departing from the gist of the present invention.
이하에서 설명되는 본 명세서 및 청구범위에 사용된 용어나 단어는 통상적이거나 사전적인 의미로 한정해서 해석되어서는 아니 되며, 발명자는 그 자신의 발명을 가장 최선의 방법으로 설명하기 위해 용어의 개념으로 적절하게 정의할 수 있다는 원칙에 입각하여 본 발명의 기술적 사상에 부합하는 의미와 개념으로 해석되어야만 한다. 따라서 본 명세서에 기재된 실시예와 도면에 도시된 구성은 본 발명의 바람직한 실시예에 불과할 뿐이고, 본 발명의 기술적 사상을 모두 대변하는 것은 아니므로, 본 출원시점에 있어서 이들을 대체할 수 있는 다양한 균등물과 변형예들이 있을 수 있음을 이해하여야 한다.The terms or words used in this specification and claims described below should not be construed as being limited to ordinary or dictionary meanings, and the inventors have appropriately used the concept of terms to describe their inventions in the best way. It should be interpreted as a meaning and concept consistent with the technical spirit of the present invention based on the principle that it can be defined in the following way. Therefore, the embodiments described in this specification and the configurations shown in the drawings are only preferred embodiments of the present invention, and do not represent all of the technical spirit of the present invention, so various equivalents that can replace them at the time of the present application. It should be understood that there may be variations and variations.
이하, 본 발명을 보다 상세하게 설명하면 다음과 같다.Hereinafter, the present invention will be described in more detail as follows.
본 발명은 전기화학소자용 전해액에 첨가되는 첨가제 및 그를 포함하는 전해액에 관한 것이다.The present invention relates to an additive added to an electrolyte solution for an electrochemical device and an electrolyte solution containing the same.
여기서 전기화학소자는 슈퍼 커패시터를 포함한다.Here, the electrochemical device includes a supercapacitor.
본 발명에 따른 전해액은 전해질, 용매 및 첨가제를 포함한다. 첨가제는 아래의 화학식 1로 표시되는 옥타메틸사이클로테트라실록산(octamethylcyclotetrasiloxane)을 사용한다.The electrolyte solution according to the present invention includes an electrolyte, a solvent and an additive. As an additive, octamethylcyclotetrasiloxane represented by Formula 1 below is used.
[화학식 1][Formula 1]
전해질은 슈퍼 커패시터에 적용되는 전해질일 수 있다. 예컨대 전해질은 SBPBF4(spirobipyrrolidinium tetrafluoroborate), TEABF4(tetraethylammonium tetrafluorborate), TEMABF4(triethylmethylammonium tetrafluorborate), EMIBF4(1-ethyl-3-methyl imidazolium tetrafluoborate), EMITFSI(1-ethyl-3-methyl imidazolium bis(trifluoromethane sulfonyl)imide), LiClO4, LiPF6, LiAsF6, 또는 LiBF4를 포함할 수 있다. 전해질의 농도는 0.5M 내지 10M 이며, 바람직하게는 0.5M 내지 3M일 수 있다. 예컨대 전해질로는, 화학식 2로 표시되는, 1M SBPBF4이 사용될 수 있다.The electrolyte may be an electrolyte applied to a supercapacitor. For example, electrolytes include SBPBF 4 (spirobipyrrolidinium tetrafluoroborate), TEABF 4 (tetraethylammonium tetrafluorborate), TEMABF 4 (triethylmethylammonium tetrafluorborate), EMIBF 4 (1-ethyl-3-methyl imidazolium tetrafluoroborate), EMITFSI (1-ethyl-3-methyl imidazolium bis( trifluoromethane sulfonyl)imide), LiClO 4 , LiPF 6 , LiAsF 6 , or LiBF 4 . The concentration of the electrolyte may be 0.5M to 10M, preferably 0.5M to 3M. For example, as an electrolyte, 1M SBPBF 4 represented by Formula 2 may be used.
[화학식 2][Formula 2]
용매로는 화학식 3으로 표시되는 SL(Sulfolane)과 화학식 4로 표시되는 AN(acetonitrile)의 혼합 용매를 사용하였다.As a solvent, a mixed solvent of SL (Sulfolane) represented by Chemical Formula 3 and AN (acetonitrile) represented by Chemical Formula 4 was used.
[화학식 3][Formula 3]
[화학식 4][Formula 4]
여기서 SL은 AN 보다 점도가 높으므로 AN과 SL을 혼합하여 사용할 경우, 초기 AC-ESR(equivalence series resistance; 등가직렬저항)은 AN만 사용할 경우보다 크지만, SL의 끓는점(285℃)이 AN의 끓는점(82℃) 보다 높으므로 SL과 AN을 혼합하여 사용할 경우 고온 고습 환경에서 저항 증가율을 감소시킬 수 있기 때문이다.Here, since SL has a higher viscosity than AN, when AN and SL are mixed together, the initial AC-ESR (equivalence series resistance) is greater than when AN alone is used, but the boiling point (285℃) of SL is higher than that of AN. This is because it is higher than the boiling point (82℃), so the resistance increase rate can be reduced in a high temperature and high humidity environment when SL and AN are mixed and used.
이와 같이 저항 증가율을 감소시키기 위한 용매의 조성비는 SL 10 내지 50 wt%와, AN 50 내지 90 wt% 일 수 있다.In this way, the composition ratio of the solvent for reducing the resistance increase rate may be 10 to 50 wt% of SL and 50 to 90 wt% of AN.
반면에 용매로 AN 및 SL 중에 하나를 사용할 경우, 전해액에 옥타메틸사이클로테트라실록산을 첨가제로 첨가하더라도, 첨가제 첨가로 인한 저항증가율과 용량감소율의 개선이 미미하거나 퇴보할 수 있다. 즉 후술되겠지만 용매로 AN을 단독으로 사용하고 첨가제로 옥타메틸사이클로테트라실록산을 사용한 전해액이, AN 및 SL의 혼합 용매를 사용하면서 첨가제를 첨가하지 않은 전해액 보다, 저항증가율과 용량감소율이 퇴보할 수 있다.On the other hand, when using one of AN and SL as a solvent, even if octamethylcyclotetrasiloxane is added as an additive to the electrolyte, the improvement in the resistance increase rate and the capacity decrease rate due to the addition of the additive may be insignificant or degenerate. That is, as will be described later, an electrolyte solution using AN alone as a solvent and octamethylcyclotetrasiloxane as an additive may have a higher rate of resistance increase and a lower rate of capacity decrease than an electrolyte solution using a mixed solvent of AN and SL and no additive added. .
그리고 첨가제로 옥타메틸사이클로테트라실록산을 사용함으로써, 전기화학소자의 고온 고습 환경에서의 저항증가율과 용량감소율을 개선할 수 있다. 전해액에 첨가제로 옥타메틸사이클로테트라실록산이 5 wt% 미만이 첨가될 수 있다. 옥타메틸사이클로테트라실록산이 5 wt% 이상 첨가될 경우, 저항증가율과 용량감소율이 퇴보할 수 있다.In addition, by using octamethylcyclotetrasiloxane as an additive, it is possible to improve the resistance increase rate and the capacity decrease rate of the electrochemical device in a high-temperature, high-humidity environment. Octamethylcyclotetrasiloxane may be added in an amount of less than 5 wt% as an additive to the electrolyte solution. When octamethylcyclotetrasiloxane is added in an amount of 5 wt% or more, the resistance increase rate and the capacity decrease rate may deteriorate.
바람직하게는 전해액에 첨가제로 옥타메틸사이클로테트라실록산이 0.5 내지 1 wt%가 첨가될 수 있다. 즉 첨가제가 1 wt% 이하로 첨가될 때, 저항증가율과 용량감소율의 개선 효과를 기대할 수 있다. 그리고 첨가제가 0.5 wt% 미만으로 첨가될 경우, 첨가제 첨가로 인한 저항증가율과 용량감소율의 개선이 미미할 수 있다.Preferably, 0.5 to 1 wt% of octamethylcyclotetrasiloxane may be added to the electrolyte as an additive. That is, when the additive is added in an amount of 1 wt% or less, the effect of improving the resistance increase rate and the capacity decrease rate can be expected. In addition, when the additive is added in an amount of less than 0.5 wt%, the improvement in the resistance increase rate and the capacity decrease rate due to the addition of the additive may be insignificant.
[실시예 및 비교예][Examples and Comparative Examples]
이와 같은 본 발명에 따른 전해액의 전기화학적 특성을 확인하기 위해서, 아래의 표 1과 같이 실시예 및 비교예에 따른 전해액을 제조하였다. 제조된 실시예 및 비교예에 따른 전해액을 포함하는 전기화학소자를 제조하여 85℃ 및 85%RH에서 2.7V를 인가하면서 고온고습 부하 테스트를 진행하였다. 고온고습 부하 테스트 결과를 표 1에 기재하였다. 비교예 및 실시예에 따른 전기화학소자는 EDLC로 직경 10mm 및 높이 30mm로 제조하였다.In order to confirm the electrochemical characteristics of the electrolyte solution according to the present invention, electrolyte solutions according to Examples and Comparative Examples were prepared as shown in Table 1 below. An electrochemical device including the electrolyte solution according to the prepared Examples and Comparative Examples was manufactured, and a high-temperature, high-humidity load test was performed while applying 2.7V at 85 ° C. and 85% RH. The high temperature and high humidity load test results are shown in Table 1. Electrochemical devices according to Comparative Examples and Examples were manufactured with a diameter of 10 mm and a height of 30 mm by EDLC.
표 1을 참조하면, 비교예1에 따른 첨가제가 첨가되지 않은 전해액은 전해질 1M SBPBF4과 용매 AN과 SL을 포함한다.Referring to Table 1, the electrolyte solution to which no additives were added according to Comparative Example 1 includes an electrolyte 1M SBPBF 4 and solvents AN and SL.
실시예1에 따른 전해액은 비교예1에 따른 전해액에 첨가제가 0.5 wt%가 첨가된다. 실시예2에 따른 전해액은 비교예1에 따른 전해액에 첨가제가 1 wt%가 첨가된다.In the electrolyte solution according to Example 1, 0.5 wt% of the additive was added to the electrolyte solution according to Comparative Example 1. In the electrolyte solution according to Example 2, 1 wt% of the additive was added to the electrolyte solution according to Comparative Example 1.
비교예1에 따른 전해액을 기준으로 하여 실시예1, 실시예2, 비교예2 및 비교예3에 따른 전해액을 포함하는 전기화학소자에 대한 고온고습 부하 테스트를 진행하여 AC-ESR과 커패시턴스(Capacitance)를 평가하였다.Based on the electrolyte according to Comparative Example 1, a high-temperature and high-humidity load test was performed on the electrochemical device including the electrolyte according to Example 1, Example 2, Comparative Example 2, and Comparative Example 3 to measure AC-ESR and capacitance ) was evaluated.
고온고습 부하 테스트 결과, 실시예2에 따른 전해액이 1000 시간(hr)에서 비교예1에 따른 전해액 대비하여 AC-ESR이 약 6.8% 감소했으며, 커패시턴스(Capacitance)가 약 2.9% 상승한 것을 확인할 수 있다.As a result of the high temperature and high humidity load test, it can be confirmed that the electrolyte according to Example 2 decreased by about 6.8% in AC-ESR and increased in capacitance by about 2.9% compared to the electrolyte according to Comparative Example 1 at 1000 hours (hr). .
고온고습 부하 테스트 결과, 첨가제를 0.5 wt%를 첨가한 실시예1 보다 첨가제를 1 wt%를 첨가한 실시예2가 고온고습 환경에서 AC-ESR 및 커패시턴스 특성이 개선된 것을 확인할 수 있다.As a result of the high temperature and high humidity load test, it can be seen that the AC-ESR and capacitance characteristics of Example 2 in which 1 wt% of the additive is added are improved compared to Example 1 in which 0.5 wt% of the additive is added.
하지만 첨가제를 5 wt%를 첨가한 비교예2의 경우, 비교예1 대비 AC-ESR이 약 14.1% 증가하고, 커패시턴스가 약 13.4% 감소한 것을 확인할 수 있다.However, in the case of Comparative Example 2 in which 5 wt% of the additive was added, it can be seen that the AC-ESR increased by about 14.1% and the capacitance decreased by about 13.4% compared to Comparative Example 1.
따라서 전해액에 첨가되는 첨가제의 양은 5 wt% 미만이 바람직한 것을 확인할 수 있다.Therefore, it can be seen that the amount of the additive added to the electrolyte solution is preferably less than 5 wt%.
그리고 전해액의 용매로 AN을 단독으로 사용하고, 첨가제를 1 wt%를 첨가한 비교예3의 경우, 비교예1 대비 AC-ESR이 약 965.2% 증가하고, 커패시턴스가 약 95.2% 감소한 것을 확인할 수 있다.And in the case of Comparative Example 3 in which AN was used alone as the solvent of the electrolyte and 1 wt% of the additive was added, it can be seen that the AC-ESR increased by about 965.2% and the capacitance decreased by about 95.2% compared to Comparative Example 1. .
따라서 전해액의 용매로는 AN과 SL의 혼합 용매를 사용하는 것이 바람직한 것을 확인할 수 있다.Therefore, it can be confirmed that it is preferable to use a mixed solvent of AN and SL as the solvent of the electrolyte solution.
이와 같이 실시예1 및 2에 따른 전해액은 고온고습 부하 테스트에서 저항증가율과 용량감소율이 개선된 것을 확인할 수 있다. 이것은 옥타메틸사이클로테트라실록산을 첨가제로 전해액에 첨가함으로써, 실시예1 및 2에 따른 전해액을 사용하는 전기화학소자의 작동 온도가 확장되었음을 의미한다.As such, it can be confirmed that the electrolyte solutions according to Examples 1 and 2 improved the resistance increase rate and the capacity decrease rate in the high-temperature, high-humidity load test. This means that by adding octamethylcyclotetrasiloxane as an additive to the electrolyte solution, the operating temperature of the electrochemical device using the electrolyte solution according to Examples 1 and 2 was extended.
한편, 본 명세서와 도면에 개시된 실시예들은 이해를 돕기 위해 특정 예를 제시한 것에 지나지 않으며, 본 발명의 범위를 한정하고자 하는 것은 아니다. 여기에 개시된 실시예들 이외에도 본 발명의 기술적 사상에 바탕을 둔 다른 변형예들이 실시 가능하다는 것은, 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자에게는 자명한 것이다.On the other hand, the embodiments disclosed in this specification and drawings are only presented as specific examples to aid understanding, and are not intended to limit the scope of the present invention. In addition to the embodiments disclosed herein, it is obvious to those skilled in the art that other modifications based on the technical idea of the present invention can be implemented.
Claims (8)
SBPBF4(spirobipyrrolidinium tetrafluoroborate)의 전해질;
SL(Sulfolane) 및 AN(acetonitrile)이 혼합된 용매; 및
상기 슈퍼 커패시터의 저항증가율과 용량감소율을 개선하여 상기 슈퍼 커패시터의 작동 온도를 확장하기 위해서 첨가되는 옥타메틸사이클로테트라실록산(octamethylcyclotetrasiloxane)의 첨가제;로 구성되며,
상기 옥타메틸사이클로테트라실록산은 0.5 내지 1 wt%가 첨가되고,
상기 용매는 상기 SL 10 내지 50 wt%와, 상기 AN 50 내지 90 wt%로 구성된 것을 특징으로 하는 슈퍼 커패시터용 전해액.As an electrolyte for a supercapacitor,
electrolyte of SBPBF 4 (spirobipyrrolidinium tetrafluoroborate);
A solvent in which SL (Sulfolane) and AN (acetonitrile) are mixed; and
An additive of octamethylcyclotetrasiloxane added to extend the operating temperature of the supercapacitor by improving the resistance increase rate and capacity decrease rate of the supercapacitor;
0.5 to 1 wt% of the octamethylcyclotetrasiloxane is added,
The solvent is an electrolyte solution for a supercapacitor, characterized in that composed of 10 to 50 wt% of the SL and 50 to 90 wt% of the AN.
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KR20090113836A (en) * | 2007-03-28 | 2009-11-02 | 산요가세이고교 가부시키가이샤 | Electrolyte, and electrolyte solution or electrochemical element comprising the same |
KR20180091585A (en) * | 2017-02-07 | 2018-08-16 | 서울시립대학교 산학협력단 | Cross-linked polymer for gel polymer electrolyte and manufacturing therof, gel polymer electrolyte and manufacturing therof, and electrochemical device including the same gel polymer electrolyte |
KR20200141119A (en) * | 2019-06-10 | 2020-12-18 | 주식회사 엘지화학 | Electrode protection layer for lithium secondary battery and method for preparing the same |
KR102188237B1 (en) * | 2019-10-31 | 2020-12-08 | 코칩 주식회사 | Composite for supercapacitor electrode, manufacturing method of supercapacitor electrode using the composite, and supercapacitor manufactured by the method |
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인용발명 1: 등록특허공보 제10-2188237호(2020.12.08.) 1부.* |
인용발명 2: 공개특허공보 제10-2020-0141119호(2020.12.18.) 1부.* |
인용발명 3: 공개특허공보 제10-2009-0113836호(2009.11.02.) 1부.* |
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