KR20120099943A - Electrolyte composition and lithium ion capacitor including the same - Google Patents
Electrolyte composition and lithium ion capacitor including the same Download PDFInfo
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- KR20120099943A KR20120099943A KR1020110018484A KR20110018484A KR20120099943A KR 20120099943 A KR20120099943 A KR 20120099943A KR 1020110018484 A KR1020110018484 A KR 1020110018484A KR 20110018484 A KR20110018484 A KR 20110018484A KR 20120099943 A KR20120099943 A KR 20120099943A
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- lithium ion
- ion capacitor
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 40
- 239000003792 electrolyte Substances 0.000 title claims abstract description 38
- 239000003990 capacitor Substances 0.000 title claims abstract description 34
- 239000000203 mixture Substances 0.000 title claims abstract description 25
- 239000002608 ionic liquid Substances 0.000 claims abstract description 19
- -1 1-ethyl-3-methylimidazolium fluorine sulfonyl amide Chemical compound 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003960 organic solvent Substances 0.000 claims abstract description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 8
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000011149 active material Substances 0.000 claims abstract description 7
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims abstract description 6
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims abstract description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims abstract description 4
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims abstract description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 22
- 239000008151 electrolyte solution Substances 0.000 claims description 14
- 229910052744 lithium Inorganic materials 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 7
- 229910000733 Li alloy Inorganic materials 0.000 claims description 4
- 229910013870 LiPF 6 Inorganic materials 0.000 claims description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 4
- 239000001989 lithium alloy Substances 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 229910013063 LiBF 4 Inorganic materials 0.000 claims description 3
- 229910013684 LiClO 4 Inorganic materials 0.000 claims description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 3
- 229910000552 LiCF3SO3 Inorganic materials 0.000 abstract 1
- 229910001290 LiPF6 Inorganic materials 0.000 abstract 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 abstract 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 abstract 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 abstract 1
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 abstract 1
- 229920000379 polypropylene carbonate Polymers 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 229940021013 electrolyte solution Drugs 0.000 description 8
- 239000011888 foil Substances 0.000 description 5
- 229910003002 lithium salt Inorganic materials 0.000 description 5
- 159000000002 lithium salts Chemical class 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000007773 negative electrode material Substances 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 4
- 239000007774 positive electrode material Substances 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000005001 laminate film Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 230000000149 penetrating effect Effects 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- MYWGVEGHKGKUMM-UHFFFAOYSA-N carbonic acid;ethene Chemical compound C=C.C=C.OC(O)=O MYWGVEGHKGKUMM-UHFFFAOYSA-N 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000002006 petroleum coke Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
- H01G11/58—Liquid electrolytes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/04—Hybrid capacitors
- H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Secondary Cells (AREA)
Abstract
Description
본 발명은 전해액 조성물 및 이를 포함하는 리튬 이온 캐패시터에 관한 것이다.
The present invention relates to an electrolyte composition and a lithium ion capacitor including the same.
리튬 이온 캐패시터 제조를 위해서는 프리 도프 공정이 필요함으로, 제조비용이 비싸져서 제조에 곤란이 있다. In order to manufacture a lithium ion capacitor, a free dope process is required, and thus, manufacturing costs are high, and thus manufacturing is difficult.
전자기기용, 전력저장용, 이동체용 전원 등을 주된 용도로 하여 개발?실용화되고 있는 리튬 이온 이차전지는 고에너지 밀도를 가지는 특징을 가진 주요 제품이다. 리튬 이온 이차전지에 이용되어 있는 전해액은, 일반적으로 휘발성이 있는 가연성의 유기용매(예를 들면, 에틸렌 카보네이트 또는 디에틸렌 카보네이트 등)에 리튬염 (예를 들면, LiPF 등)을 용해시켜 제조된다. 그러나, 잘못된 사용에서나 고온환경 하에서의 안전성 확보를 위해 전지 시스템에 기구적으로 보호 회로 등의 안전대책이 필요한 형편이다. Lithium ion secondary batteries, which have been developed and put into practical use mainly for electronic devices, power storage, and mobile power supplies, are the main products with high energy density. The electrolyte solution used for a lithium ion secondary battery is manufactured by melt | dissolving a lithium salt (for example, LiPF etc.) in the volatile combustible organic solvent (for example, ethylene carbonate or diethylene carbonate etc.) generally. However, safety measures such as protection circuits are required for the battery system in order to secure safety in a high temperature environment.
리튬 이온 캐패시터의 경우, 일반적으로 음극에는 리튬 이온을 인터칼레이트 할 수 있는 탄소재료가 사용되고 있지만, 원래 리튬 금속 또는 그 합금을 이용하는 것이 에너지 밀도적으로 보다 유리하다. 그러나, 리튬 및 리튬 금속을 음극으로서 채용하는 경우 충방전의 반복과 함께 전해액의 발화 문제가 있다. In the case of a lithium ion capacitor, a carbon material capable of intercalating lithium ions is generally used for the negative electrode, but it is more advantageous in terms of energy density to use lithium metal or an alloy thereof. However, when lithium and lithium metal are used as the negative electrode, there is a problem of ignition of the electrolyte solution with repeated charge and discharge.
따라서, 이러한 구조적인 조건 하에서도 고용량의 리튬 이온 캐패시터의 특성을 가지면서도 전해액이 발화되지 않는 안전성이 향상된 리튬 이온 캐패시터의 개발이 시급하다. Therefore, there is an urgent need to develop a lithium ion capacitor with improved safety that does not ignite the electrolyte while having the characteristics of a high capacity lithium ion capacitor even under such structural conditions.
이러한 종래 기술을 살피면, 리튬염과 이온성 액체만으로 구성되는 전해액을 적용하는 것에 의해 높은 안전성을 나타내는 리튬(이온)이차전지를 제안해 왔다. 그러나, 리튬염과 이온성 액체만으로 구성되는 전해액은 기존의 일반 유기 용매를 사용하는 것에 비해 점도가 높고, 고효율 방전 성능에 문제가 있다. 더욱이 대표적인 음극 활물질 재료인 그라파이트를 적용했을 경우에는, 충분한 충방전 사이클 성능을 얻을 수 없는 문제가 있었다.
In view of such a prior art, a lithium (ion) secondary battery having high safety has been proposed by applying an electrolyte composed only of a lithium salt and an ionic liquid. However, an electrolyte composed only of a lithium salt and an ionic liquid has a higher viscosity than a conventional general organic solvent and has a problem in high efficiency discharge performance. Moreover, when graphite, which is a representative negative electrode active material material, is applied, there is a problem in that sufficient charge and discharge cycle performance cannot be obtained.
따라서, 본 발명에서는 상기와 같은 종래 기술의 문제들을 해결하기 위한 것으로서, 본 발명의 목적은 특정의 이온성 액체를 사용하여 전해액 누출이 없어 안전성이 우수한 전해액 조성물을 제공하는 데 있다. Accordingly, the present invention is to solve the problems of the prior art as described above, the object of the present invention is to provide an electrolyte composition excellent in safety with no electrolyte leakage by using a specific ionic liquid.
또한, 본 발명의 다른 목적은 상기 전해액 조성물로부터 제조된 이온성 전해질막을 포함하여 리튬 이온의 프리도핑 없이도 안전성이 향상된 리튬 이온 캐패시터를 제공하는 데 있다.
In addition, another object of the present invention is to provide a lithium ion capacitor having improved safety without pre-doping of lithium ions, including the ionic electrolyte membrane prepared from the electrolyte composition.
상기 과제를 해결하기 위한 본 발명의 일 실시예에 따른 전해액 조성물은 전해액 용매로서 1-에틸-3-메틸이미다졸륨 플루오르설포닐 아미드 이온성 액체 20~50중량%, 및 유기 용매 80~50중량%로 포함할 수 있다. The electrolyte solution composition according to an embodiment of the present invention for solving the above problems is 20 to 50% by weight of 1-ethyl-3-methylimidazolium fluorsulfonyl amide ionic liquid, and 80 to 50% by weight of an organic solvent as an electrolyte solvent May contain%.
상기 유기 용매는 프로필렌카보네이트, 디에틸카보네이트, 에틸렌카보네이트, 술포란, 아세톤니트릴, 디메톡시에탄 및 테트라하이드로푸란, 및 에틸메틸카보네이트로 이루어진 그룹으로부터 선택되는 1종 이상일 수 있다. The organic solvent may be at least one selected from the group consisting of propylene carbonate, diethyl carbonate, ethylene carbonate, sulfolane, acetonitrile, dimethoxyethane and tetrahydrofuran, and ethyl methyl carbonate.
또한, 상기 전해액 조성물은 LiN(CF3SO2)2, LiCF3SO3, LiPF6, LiBF4 및LiClO4로 이루어지는 그룹으로부터 선택되는 1종 이상의 리튬 전해질염을 포함할 수 있다. In addition, the electrolyte composition may include at least one lithium electrolyte salt selected from the group consisting of LiN (CF 3 SO 2 ) 2 , LiCF 3 SO 3 , LiPF 6 , LiBF 4, and LiClO 4 .
또한, 다른 과제를 해결하기 위한 본 발명의 일 실시예에 따른 리튬 이온 캐패시터는 전해액 용매로서 1-에틸-3-메틸이미다졸륨 플루오르설포닐 아미드 이온성 액체 20~50중량%, 및 유기 용매 80~50중량%로 포함하는 전해액 조성물로부터 제조된 이온성 전해질막을 포함하는 것일 수 있다. In addition, a lithium ion capacitor according to an embodiment of the present invention for solving other problems is 20 to 50% by weight of 1-ethyl-3-methylimidazolium fluorsulfonyl amide ionic liquid as an electrolyte solvent, and an organic solvent 80 It may be to include an ionic electrolyte membrane prepared from an electrolyte solution composition containing ˜50% by weight.
상기 리튬 이온 캐패시터의 양극은 탄소계 재료를 활물질로 포함할 수 있다. The positive electrode of the lithium ion capacitor may include a carbon-based material as an active material.
본 발명의 실시예에 따르면, 상기 탄소계 재료는 비표면적이 800~3000㎡/g인 활성탄이 바람직하다. According to an embodiment of the present invention, the carbon-based material is preferably activated carbon having a specific surface area of 800 ~ 3000 m 2 / g.
또한, 상기 리튬 이온 캐패시터의 음극은 리튬 금속 및 리튬 합금의 재료를 활물질로 포함할 수 있다.
In addition, the negative electrode of the lithium ion capacitor may include a material of lithium metal and lithium alloy as the active material.
본 발명의 실시예에 따르면, 이온성 액체를 전해액 조성물에 포함함으로써 전해액 누출이 없고, 전해액 발화 문제를 억제할 수 있어 안전성이 우수한 리튬 이온 캐패시터를 제공할 수 있으며, 음극 활물질로서 리튬 금속 및 리튬 합금을 이용하여 프리 도핑의 공정 없이도 고용량의 리튬 이온 캐패시터를 제조할 수 있다.
According to an embodiment of the present invention, by including an ionic liquid in the electrolyte composition, there is no leakage of electrolyte and suppresses the problem of ignition of electrolyte, thereby providing a lithium ion capacitor having excellent safety, and providing a lithium metal and a lithium alloy as a negative electrode active material. Using a high capacity lithium ion capacitor can be produced without the pre-doping process.
본 명세서에서 사용된 용어는 특정 실시예를 설명하기 위하여 사용되며, 본 발명을 제한하기 위한 것이 아니다. 본 명세서에서 사용된 바와 같이, 단수 형태는 문맥상 다른 경우를 분명히 지적하는 것이 아니라면, 복수의 형태를 포함할 수 있다. 또한, 본 명세서에서 사용되는 경우 "포함한다(comprise)" 및/또는 "포함하는(comprising)"은 언급한 형상들, 숫자, 단계, 동작, 부재, 요소 및/또는 이들 그룹의 존재를 특정하는 것이며, 하나 이상의 다른 형상, 숫자, 동작, 부재, 요소 및/또는 그룹들의 존재 또는 부가를 배제하는 것이 아니다.The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the singular forms "a", "an" and "the" may include the plural forms as well, unless the context clearly indicates otherwise. Also, as used herein, "comprise" and / or "comprising" specifies the presence of the mentioned shapes, numbers, steps, actions, members, elements and / or groups of these. It is not intended to exclude the presence or the addition of one or more other shapes, numbers, acts, members, elements and / or groups.
본 발명은 난연성 이온성 액체를 포함하는 전해액 조성물과, 이를 포함하여 안전성이 우수한 고용량의 리튬 이온 캐패시터에 관한 것이다.The present invention relates to an electrolyte composition comprising a flame retardant ionic liquid and a high capacity lithium ion capacitor having excellent safety.
본 발명에 따른 전해액 조성물은 리튬 이온 캐패시터에 사용되는 것으로, 전해질염과 용매를 포함하며, 본 발명에서는 특별히 상기 용매로서 이온성 액체인 1-에틸-3-메틸이미다졸륨 플루오르설포닐 아미드를 전체 용매 중 20~50중량%로 포함하는 데 특징을 가진다. The electrolyte composition according to the present invention is used in a lithium ion capacitor, and includes an electrolyte salt and a solvent. In the present invention, the ionic liquid 1-ethyl-3-methylimidazolium fluorsulfonyl amide is specifically used as the solvent. It is characterized by including in 20 to 50% by weight of the solvent.
이온성 액체는 상온에서도 액체 상태를 나타내는 이온성 물질의 총칭이며, 불휘발성, 난연소성의 뛰어난 특징을 가지고 있다. 따라서, 이러한 특징을 가지는 이온성 액체를 전해액 조성물에서 용매로 이용하는 경우에는 전해액의 발화문제를 억제하는 효과를 가진다. Ionic liquids are generic terms for ionic materials that exhibit a liquid state even at room temperature, and have excellent characteristics of nonvolatile and flame retardant properties. Therefore, when an ionic liquid having such characteristics is used as a solvent in the electrolyte composition, it has an effect of suppressing the problem of ignition of the electrolyte.
이온성 액체는 종래의 전해질 용액을 대신하고, 각종 전기화학 디바이스용 전해질에의 적용의 가능성이 높은 재료로서 최근 주목 받고 있다. Ionic liquids have recently attracted attention as materials which have a high possibility of being applied to electrolytes for various electrochemical devices instead of the conventional electrolyte solutions.
따라서, 본 발명에서는 전해액에서 이온성 액체에 의한 난연소성 발현 효과와, 리튬 이온 캐패시터에 적용했을 때의 유기용매에 의한 성능향상의 두 가지 효과를 가지도록 하였다. Therefore, in the present invention, it has two effects of the flame retardancy expression effect by the ionic liquid in the electrolyte solution and the performance improvement by the organic solvent when applied to the lithium ion capacitor.
본 발명에서는 이온성 액체로서 1-에틸-3-메틸이미다졸륨 플루오르설포닐 아미드를 전체 용매 중 20~50중량%로 포함되는 것이 바람직하며, 전체 용매 중 20중량% 미만인 경우 전도성이 낮아짐으로 저항특성에 문제가 생길 수 있고 50중량%를 초과하는 경우 점도 상승에 의하여서 저항이 높아짐으로 바람직하지 못하다. In the present invention, it is preferable to include 1-ethyl-3-methylimidazolium fluorsulfonyl amide in an amount of 20 to 50% by weight in the total solvent, and less than 20% by weight in the total solvent. Problems may occur in the properties, and if it exceeds 50% by weight, the resistance is increased due to the viscosity increase, which is not preferable.
상기 이온성 액체와 혼합 사용되는 용매는 통상의 유기 용매, 구체적으로는 프로필렌카보네이트, 디에틸카보네이트, 에틸렌카보네이트, 술포란, 아세톤니트릴, 디메톡시에탄 및 테트라하이드로푸란, 및 에틸메틸카보네이트로 이루어진 그룹으로부터 선택되는 1종 이상으로서, 전체 용매 중 80~50중량%로 포함될 수 있다. The solvent used in admixture with the ionic liquid is a conventional organic solvent, specifically from the group consisting of propylene carbonate, diethyl carbonate, ethylene carbonate, sulfolane, acetonitrile, dimethoxyethane and tetrahydrofuran, and ethyl methyl carbonate As one or more selected, it may be included in 80 to 50% by weight of the total solvent.
또한, 본 발명에 따른 전해액 조성물에서 전해질염은 리튬염 또는 암모늄염 등일 수 있다. 리튬염의 예로서는 LiN(CF3SO2)2, LiCF3SO3, LiPF6, LiBF4 및LiClO4로 이루어지는 그룹으로부터 선택되는 1종 이상이나, 이에 한정되는 것은 아니다. In addition, the electrolyte salt in the electrolyte composition according to the present invention may be a lithium salt or an ammonium salt. Examples of lithium salts include one or more selected from the group consisting of LiN (CF 3 SO 2 ) 2 , LiCF 3 SO 3 , LiPF 6 , LiBF 4, and LiClO 4 , but are not limited thereto.
또한, 본 발명은 상기 전해액 조성물을 포함하는 리튬 이온 캐패시터를 제공한다. In addition, the present invention provides a lithium ion capacitor comprising the electrolyte composition.
본 발명에 따른 리튬 이온 커패시터는 기본적으로 양극과 음극이 분리막으로 절연되어 구성된 전극 셀에 전해액을 함침시킨 다음, 이를 외장재 케이스에 수납된 구조를 가진다. The lithium ion capacitor according to the present invention basically has a structure in which an electrolyte is impregnated into an electrode cell in which an anode and a cathode are insulated with a separator, and then housed in an exterior case.
여기서, 상기 전극 셀은 분리막을 사이에 두고 양극과 음극이 교대로 반복되는 구조를 가진다. 상기 양극과 음극은 각 전극 집전체의 일면 또는 양면에 전극 활물질층이 도포된 구조를 가진다.Here, the electrode cell has a structure in which the anode and the cathode are alternately repeated with a separator interposed therebetween. The positive electrode and the negative electrode have a structure in which an electrode active material layer is coated on one or both surfaces of each electrode current collector.
본 발명에 따른 음극의 집전체로는 스테인레스 스틸, 동, 니켈, 및 이들의 합금으로 이루어진 그룹으로부터 선택되는 1종 이상일 수 있으며, 이 중에서 동이 가장 바람직하다. 또한, 상기와 같은 금속의 박뿐만 아니라, 에칭된 금속박, 혹은 확장 메탈, 펀칭 메탈, 그물, 발포체 등과 같이 표면을 관통하는 구멍을 갖춘 것이어도 좋다. 상기 집전체의 두께는 10~300㎛ 정도의 것이 바람직하다. The current collector of the negative electrode according to the present invention may be one or more selected from the group consisting of stainless steel, copper, nickel, and alloys thereof, of which copper is most preferred. In addition to the foil of the metal as described above, an etched metal foil or a hole penetrating the surface may be provided such as expanded metal, punched metal, net, foam or the like. It is preferable that the thickness of the said collector is about 10-300 micrometers.
본 발명에 따른 음극 활물질은 리튬 금속 및 리튬 합금의 재료를 활물질로 포함할 수 있으며, 또한 리튬 금속의 판과 음극 집전체를 압연시켜 시트상의 음극을 얻을 수도 있다.The negative electrode active material according to the present invention may include a material of lithium metal and lithium alloy as the active material, and may also be obtained by rolling a sheet of the lithium metal and the negative electrode current collector to obtain a sheet-like negative electrode.
본 발명에 따른 양극은 알루미늄, 스텐레스, 티타늄, 탄탈(tantale), 및 니오브(niobium)로 이루어진 그룹으로부터 선택되는 1종 이상의 양극 집전체 상에 양극 활물질을 도포시켜 제조된다. 상기 집전체 중에서 알루미늄이 가장 바람직하나, 이에 한정되는 것은 아니다. 또한, 상기와 같은 금속의 박뿐만 아니라, 에칭된 금속박, 혹은 확장 메탈, 펀칭 메탈, 그물, 발포체 등과 같이 표면을 관통하는 구멍을 갖춘 것이어도 좋다. 상기 집전체의 두께는 10~300㎛ 정도의 것이 바람직하다.The positive electrode according to the present invention is prepared by applying a positive electrode active material on at least one positive electrode current collector selected from the group consisting of aluminum, stainless steel, titanium, tantale, and niobium. Aluminum is the most preferred among the current collector, but is not limited thereto. In addition to the foil of the metal as described above, an etched metal foil or a hole penetrating the surface may be provided such as expanded metal, punched metal, net, foam or the like. It is preferable that the thickness of the said collector is about 10-300 micrometers.
본 발명의 양극 활물질은 탄소계 재료가 바람직하며, 탄소계 재료 중에서도 비표면적이 큰 활성탄이 바람직하다. 본 발명에 따른 활성탄은 비표면적이 800~3000㎡/g인 것이 바람직하다. 활성탄의 원료로서는, 야자 찌꺼기, 페놀 수지, 석유 콕스 등을 들 수 있고, 수증기부활법, 용융KOH부활법 등에 의해 부활되는 것이 바람직하다.The positive electrode active material of the present invention is preferably a carbon-based material, and activated carbon having a large specific surface area is preferable among the carbon-based materials. The activated carbon according to the present invention preferably has a specific surface area of 800 to 3000 m 2 / g. Examples of the raw material of the activated carbon include palm waste, phenol resins, petroleum coke and the like, and it is preferable that the activated carbon is reactivated by the steam regeneration method or the molten KOH regeneration method.
또한, 상기 양극에는 저항을 낮게 하기 위해서 전기 전도성의 카본블랙(carbon black) 또는 흑연을 포함시키는 것이 바람직하다. In addition, it is preferable to include carbon black or graphite of electrical conductivity in the anode in order to lower the resistance.
본 발명에 따른 양극의 제조 방법은, 활성탄을 바인더를 이용해 시트상으로 성형해 집전체에 도전성 접착제를 이용해 접합하는 방법이 있다. 또한 바인더에 활성탄을 분산시켜, 닥터 블레이드 법 등에 의해서 집전체에 도포 및 건조해 얻는 방법도 있으며, 본 발명을 적용하기에 모두 바람직하고, 특별히 한정되지 않는다.The manufacturing method of the positive electrode which concerns on this invention has the method of shape | molding activated carbon into a sheet form using a binder, and bonding to an electrical power collector using a conductive adhesive. Moreover, there also exists a method of disperse | distributing activated carbon to a binder and apply | coating and drying it to an electrical power collector by the doctor blade | blade method, etc., In order to apply this invention, all are preferable and it does not specifically limit.
상기 바인더는 폴리에틸렌 테트라플루오로에틸렌(tetrafluoroethylene), 폴리에틸렌 불화비닐리덴, 폴리아미드이미드, 폴리이미드 등이 있으나, 이에 한정되는 것은 아니다. The binder may include polyethylene tetrafluoroethylene, polyethylene vinylidene fluoride, polyamideimide, polyimide, and the like, but is not limited thereto.
본 발명 양극, 음극은 활물질 슬러리 제조시, 바인더 및 도전성 재료 등을 추가로 포함할 수 있고, 그 종류 및 함량은 특별히 한정되지 않고, 통상의 리튬 이온 캐패시터에 포함되는 수준이면 충분하다.The positive electrode and the negative electrode of the present invention may further include a binder, a conductive material, and the like in the preparation of the active material slurry, and the type and content thereof are not particularly limited, and a level included in a conventional lithium ion capacitor is sufficient.
이하에서 본 발명의 일 실시예에 따른 리튬 이온 캐패시터의 제조방법을 설명하면, 음극 집전체 상에 음극 활물질을 도포시켜 음극을 제조하는 단계; 양극 집전체 상에 양극 활물질을 도포시켜 양극을 제조하는 단계; 및 상기 양극과 음극을 분리막으로 절연시키고, 전해액을 함침시켜 외장형 케이스에 수납시키는 단계를 포함할 수 있다. Hereinafter, a method of manufacturing a lithium ion capacitor according to an embodiment of the present invention may include: preparing a negative electrode by applying a negative electrode active material on a negative electrode current collector; Preparing a positive electrode by coating a positive electrode active material on the positive electrode current collector; And insulating the positive electrode and the negative electrode with a separator and impregnating an electrolyte solution to accommodate the external case.
본 발명에서는 음극 활물질로서 리튬 금속 함유 물질을 사용함으로써 음극에 별도의 리튬 금속의 프리 도핑 공정이 필요하지 않다.In the present invention, by using a lithium metal-containing material as the negative electrode active material, a separate pre-doping step of the lithium metal is not required for the negative electrode.
또한, 본 발명에 따른 전해액은 이온성 액체를 포함함으로써 전해액의 누출이나 발화 가능성을 최소화시켜, 안전성이 우수한 리튬 이온 캐패시터를 제공할 수 있다. In addition, the electrolyte according to the present invention includes an ionic liquid to minimize the possibility of leakage or ignition of the electrolyte, thereby providing a lithium ion capacitor having excellent safety.
또한, 본 발명에 따른 외장형 케이스는 두 장의 금속 라미네이트 필름을 열융착하여 형성된 파우치 타입인 것이 바람직하나 특별히 이에 한정되지 않는다. 또한, 본 발명에 따른 리튬 이온 캐패시터의 형태는 특별히 한정되지 않는다.
In addition, the exterior case according to the present invention is preferably a pouch type formed by heat-sealing two sheets of metal laminate films, but is not particularly limited thereto. In addition, the form of the lithium ion capacitor which concerns on this invention is not specifically limited.
이하에서 본 발명을 실시예에 따라 기술하여 이해를 돕고자 한다. 본 발명의 실시예들은 당해 기술 분야에서 통상의 지식을 가진 자에게 본 발명을 더욱 완전하게 설명하기 위하여 제공되는 것이며, 하기 실시예는 여러 가지 다른 형태로 변형될 수 있으며, 본 발명의 범위가 하기 실시예에 한정되는 것은 아니다. 오히려, 이들 실시예는 본 개시를 더욱 충실하고 완전하게 하고, 당업자에게 본 발명의 사상을 완전하게 전달하기 위하여 제공되는 것이다.
Hereinafter, the present invention will be described in accordance with embodiments to help understand. The embodiments of the present invention are provided to more fully explain the present invention to those skilled in the art, and the following examples can be modified in various other forms, and the scope of the present invention is It is not limited to an Example. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the inventive concept to those skilled in the art.
실시예Example 1 One
이하의 실시예에 있어서, 셀의 제작은 모두 녹는점이 -60℃ 이상의 아르곤 글로브 박스(glove box) 안에서 진행하였다. In the following examples, all of the cells were fabricated in an argon glove box having a melting point of −60 ° C. or higher.
１）양극의 조제1) Preparation of anode
양극활물질로서 수증기부활법에 의해 얻은 비표면적이 약 2200㎡/g인 활성탄을 이용했다. 상기 활성탄 분말, 아세틸렌 블랙(acetylene black), 및 폴리에틸렌 불화비닐리덴을 각각 중량비 80:10:10의 비율이 되게 혼합하고, 이 혼합물을 용매인 N-메틸피롤리돈 속에 첨가하고, 교반 혼합해서 슬러리를 얻었다. 이 슬러리를 두께 20㎛의 알루미늄 박(箔) 위에 닥터 블레이드법으로 도포하고, 임시 건조한 후, 전극 사이즈가 10cm×10cm이 되게 잘라내었다. 셀의 조립 전에는, 진공에서 120℃에서 10시간 동안 건조시켰다 。
As the positive electrode active material, activated carbon having a specific surface area of about 2200 m 2 / g obtained by steam regeneration was used. The activated carbon powder, acetylene black, and polyethylene vinylidene fluoride were mixed in a ratio of 80:10:10 by weight ratio, respectively, and the mixture was added to N-methylpyrrolidone as a solvent, stirred and mixed to obtain a slurry. Got. This slurry was apply | coated on the aluminum foil of 20 micrometers in thickness by the doctor blade method, and it temporarily cut and cut out so that an electrode size might become 10 cm x 10 cm. Before assembling the cells, they were dried in vacuo at 120 ° C. for 10 hours.
2)음극의 조제2) Preparation of cathode
리튬 금속의 판과 동박의 집전체를 압연해서 음극 시트를 얻었다.
The lithium metal plate and the copper foil current collector were rolled to obtain a negative electrode sheet.
3）전해액3) electrolyte
1.3M LiPF6/50% 1-에틸-3-메틸이미다졸륨 플루오르설포닐 이온성 액체와 50% 리튬 이온 용질의 에틸렌카보네이트(EC):에틸메틸카보네이트(EMC)=1:1의 전해액 조성물을 얻었다.
An electrolyte composition of ethylene carbonate (EC): ethyl methyl carbonate (EMC) = 1: 1 of 1.3 M LiPF 6 /50% 1-ethyl-3-methylimidazolium fluorosulfonyl ionic liquid and 50% lithium ion solute was prepared. Got it.
4）리튬 이온 캐패시터 축전소자의 조립4) Assembly of lithium ion capacitor power storage element
상기 제조된 양극과 음극의 사이에 분리막(폴리프로필렌계 부직포)를 삽입하고, 여기에 상기 제조된 전해액을 함침시켜, 라미네이트 필름 케이스에 넣어서 밀봉했다. 완성된 셀은, 측정까지 약 1일 그대로 방치했다.
A separator (polypropylene-based nonwoven fabric) was inserted between the prepared positive electrode and negative electrode, and the electrolytic solution prepared above was impregnated, and placed in a laminate film case for sealing. The completed cell was left to stand for about 1 day until the measurement.
실험예Experimental Example 1 : 리튬 이온 1: lithium ion 캐패시터Capacitor 사이클 실험 Cycle experiment
정전류－정전압에서, 900초3.8Ｖ까지 충전하고, 이어서 정전류에서 2.0Ｖ까지 방전하고, 10초 경과시킨 후, 다시 같은 조건에서 충방전을 10회 반복했으며 이를 통하여서 충방전의 가능성을 확인하였다. At constant current-constant voltage, the battery was charged up to 900 seconds to 3.8 mA, and then discharged at constant current to 2.0 mA, and after 10 seconds, charging and discharging were repeated 10 times under the same conditions, thereby confirming the possibility of charge and discharge.
상기 결과로부터 본 발명의 리튬 이온 캐패시터 축전소자는, 3.8V부터 2.0V까지 충방전이 가능해서, 본 발명의 이온 액체의 전해액으로서 리튬 이온의 프리 도프없이 리튬 이온 캐패시터 축전소자의 제조가 가능한 것을 확인하였다.
From the above results, the lithium ion capacitor power storage device of the present invention can be charged and discharged from 3.8V to 2.0V, and it is confirmed that the lithium ion capacitor power storage device can be manufactured without pre-doping of lithium ions as the electrolyte solution of the ionic liquid of the present invention. It was.
Claims (7)
An electrolyte solution composition comprising 20 to 50% by weight of 1-ethyl-3-methylimidazolium fluorsulfonyl amide ionic liquid and 80 to 50% by weight of an organic solvent as an electrolyte solution solvent.
The electrolyte solution composition of claim 1, wherein the organic solvent is at least one selected from the group consisting of propylene carbonate, diethyl carbonate, ethylene carbonate, sulfolane, acetonitrile, dimethoxyethane and tetrahydrofuran, and ethyl methyl carbonate.
The electrolyte solution composition of claim 1, wherein the electrolyte solution composition comprises at least one lithium electrolyte salt selected from the group consisting of LiN (CF 3 SO 2 ) 2 , LiCF 3 SO 3 , LiPF 6 , LiBF 4, and LiClO 4 .
A lithium ion capacitor comprising the electrolyte composition according to claim 1.
The lithium ion capacitor of claim 4, wherein the anode of the lithium ion capacitor includes a carbonaceous material as an active material.
The lithium ion capacitor of claim 5, wherein the carbonaceous material is activated carbon having a specific surface area of 800 to 3000 m 2 / g.
The lithium ion capacitor of claim 4, wherein the negative electrode of the lithium ion capacitor includes a material of lithium metal and a lithium alloy as an active material.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20170178206A1 (en) * | 2015-08-10 | 2017-06-22 | Foundation Of Soongsil University-Industry Cooperation | Apparatus and method for classifying product type |
| WO2022067110A1 (en) * | 2020-09-25 | 2022-03-31 | The Board Of Trustees Of The Leland Stanford Junior University | Primary and secondary sodium and lithium batteries |
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2011
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20170178206A1 (en) * | 2015-08-10 | 2017-06-22 | Foundation Of Soongsil University-Industry Cooperation | Apparatus and method for classifying product type |
| WO2022067110A1 (en) * | 2020-09-25 | 2022-03-31 | The Board Of Trustees Of The Leland Stanford Junior University | Primary and secondary sodium and lithium batteries |
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