KR20030013851A - Electric Energy Storage System - Google Patents
Electric Energy Storage System Download PDFInfo
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- KR20030013851A KR20030013851A KR1020010048053A KR20010048053A KR20030013851A KR 20030013851 A KR20030013851 A KR 20030013851A KR 1020010048053 A KR1020010048053 A KR 1020010048053A KR 20010048053 A KR20010048053 A KR 20010048053A KR 20030013851 A KR20030013851 A KR 20030013851A
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- energy storage
- water
- storage device
- organic electrolyte
- zeolite
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- 238000004146 energy storage Methods 0.000 title claims abstract description 20
- 239000005486 organic electrolyte Substances 0.000 claims abstract description 27
- 239000010457 zeolite Substances 0.000 claims abstract description 26
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 25
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 25
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000003990 capacitor Substances 0.000 claims abstract description 8
- 239000002798 polar solvent Substances 0.000 claims abstract description 7
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims abstract description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 4
- 125000005910 alkyl carbonate group Chemical group 0.000 claims abstract description 4
- 239000002245 particle Substances 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 32
- 238000007086 side reaction Methods 0.000 abstract description 10
- 239000006227 byproduct Substances 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 6
- 239000003792 electrolyte Substances 0.000 description 14
- 239000007789 gas Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- -1 hydroxide ions Chemical class 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000012038 nucleophile Substances 0.000 description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000000010 aprotic solvent Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 229910052604 silicate mineral Inorganic materials 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-UHFFFAOYSA-N Hydrogen atom Chemical group [H] YZCKVEUIGOORGS-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000004502 linear sweep voltammetry Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
- 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
-
- 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
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
-
- 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
-
- 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)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Manufacturing & Machinery (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Power Engineering (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
Description
본 발명은 전기이중층 캐패시터나 리튬이차전지와 같은 에너지 저장 장치에 관한 것으로서, 더욱 상세하게는 유기전해질을 사용하는 전기에너지 저장 장치에 관한 것이다.The present invention relates to an energy storage device such as an electric double layer capacitor or a lithium secondary battery, and more particularly, to an electric energy storage device using an organic electrolyte.
종래의 전기이중층 캐패시터나 이차전지에서는 전압을 높이기 위해서 유기전해질을 사용하게 된다. 이는 물이 중심이 된 수용성 전해질은 물의 분해 전압이 작기 때문에 전압을 높이는데 한계가 있는 반면에 유기전해질은 분해 전압이 높기 때문에 사용 전압을 물에서보다 훨씬 더 높일 수 있기 때문이다.In a conventional electric double layer capacitor or a secondary battery, an organic electrolyte is used to increase the voltage. This is because water-based aqueous electrolytes have a limitation in increasing the voltage due to the low decomposition voltage of the water, whereas organic electrolytes can use the voltage much higher than in water due to the high decomposition voltage.
일반적으로 에너지 저장 장치에서 사용될 수 있는 유기전해질은 비프로톤성 극성 용매 (aprotic polar solvent) 이다. 용매는 보통 극성 용매와 비극성 용매로나뉘는데, 유기전해질로는 극성 용매가 사용된다. 그 이유는 전해질의 중요한 성질이 이온 전도성을 가져야 하는 것인데, 극성 용매만이 이온전도성을 가지기 때문이다. 그리고, 유기 용매 중에서도 비프로톤성 용매가 전기화학적 안정 영역이 넓다. 비프로톤성 용매는 내부에 수소 이온 (H+)이나 수산화 이온 (OH-)이 발생하지 않는 특성을 가지고 있다.In general, the organic electrolyte that can be used in the energy storage device is an aprotic polar solvent. The solvent is usually divided into a polar solvent and a nonpolar solvent. As the organic electrolyte, a polar solvent is used. The reason is that the important property of the electrolyte is to have ion conductivity, since only polar solvents have ion conductivity. In addition, among the organic solvents, the aprotic solvent has a wide range of electrochemical stability. The aprotic solvent is a hydrogen ion (H +) and hydroxide ions (OH -) in the interior has a characteristic that does not occur.
비프로톤성 유기전해질을 사용하는 에너지 저장 장치의 경우 미량의 물이 존재하면 부반응의 중요한 원인이 되는 것으로 알려져 있다. 물은 산화 환원 전위가 모두 에너지 저장 장치의 사용 전위 내에 위치하기 때문에 여러 가지 방식으로 부반응의 원인이 된다. 물의 환원 반응은 아래의 식과 같이 일어나게 된다.In the case of energy storage devices using aprotic organic electrolytes, the presence of traces of water is known to be an important cause of side reactions. Water causes side reactions in many ways because the redox potentials are all located within the use potential of the energy storage device. The reduction reaction of water occurs as shown below.
H2O + e-→ ½ H2+ OH-(2.0V vs. Li/Li+) H 2 O + e - → ½ H 2 + OH - (2.0V vs. Li / Li +)
물의 환원 반응에 의해서는 위와 같이 OH-기가 생성되는데, OH-는 비프로톤성 전해질 내에서 강한 뉴클레오파일 (nucleophile) 로서 작용하게 되어서 전해질 내의 용매와 용질의 분해 반응을 촉진하게 된다. 이러한 사실은 기존의 여러 연구들에서 이미 알려져 있는 사실이다.As a result of the reduction reaction of water, OH − groups are generated as above, and OH − acts as a strong nucleophile in the aprotic electrolyte, thereby promoting the decomposition reaction of the solvent and the solute in the electrolyte. This is already known in many existing studies.
리튬이차전지에서 가장 많이 사용하는 알킬 카보네이트계 전해질의 경우에는 상기한 반응에 따라 물에 의해서 생성되는 OH-같은 뉴클레오파일이 존재하면, 이 뉴클레오파일이 탄소와 반응하면서 알콜을 생성하고 이산화탄소를 발생시키게 된다.In the case of the alkyl carbonate electrolyte which is used most in the lithium secondary battery, if there is an OH - like nucleophile produced by water according to the above reaction, the nucleophile reacts with carbon to produce alcohol and Will be generated.
그리고 물에 의해서 형성되는 OH-는 음극 표면에서의 전해질 분해 촉진을 가져오고 탄소 표면에 부동 피막(passive film)을 형성하는 것으로 보고되어 있다.In addition, OH − formed by water has been reported to promote the decomposition of the electrolyte on the surface of the cathode and to form a passive film on the surface of the carbon.
아세토나이트릴과 같은 전해질을 사용하는 전기이중층 캐패시터에서도 상기한 바와 같은 반응은 용량 감소 및 기체 발생에 심각한 영향을 미치게 된다. 전해액 속에 형성된 OH-는 아세토나이트릴을 분해시키며 함께 들어가는 유기 암모늄계의 염을 분해시켜서 수소, 에탄 등 환원성 기체를 발생시키게 된다. 이러한 환원성 기체의 발생 기구에서 OH-등은 기체 발생의 촉매 역할을 한다. 초기 발생을 일으키고 난 다음에도 비가역적인 형태로 제거되지 않고 계속 반응을 일으키는 역할을 하게 된다.In an electric double layer capacitor using an electrolyte such as acetonitrile, the reaction as described above has a serious effect on capacity reduction and gas generation. OH - formed in the electrolyte decomposes acetonitrile and decomposes an organic ammonium salt to be introduced together to generate a reducing gas such as hydrogen and ethane. In such a mechanism for generating a reducing gas, OH - and the like serve as a catalyst for gas generation. After the initial occurrence, it is not removed in an irreversible form and continues to play a role.
물 및 그 분해 산물의 생성은 유기전해질을 사용하는 에너지 저장 장치에서 계속 되는 부반응의 촉매 물질로서 작용하기 때문에 셀의 열화에 심각한 영향을 미치게 되므로, 현재 이러한 장치의 제조 공정 중에는 물의 제거를 위해서 상당한 노력을 기울이고 있다.Since the formation of water and its decomposition products acts as a catalyst for subsequent side reactions in energy storage devices using organic electrolytes, it has a significant impact on cell deterioration. Is leaning.
본 발명에서는 상술한 문제점을 감안하여 특히 유기전해질 내에서 물 및 물에 의한 부산물로 인한 영향을 제거할 수 있도록 이들을 강하게 흡착할 수 있는 전기에너지 저장 장치를 제공하는 것을 목적으로 한다.In view of the above-described problems, an object of the present invention is to provide an electrical energy storage device capable of strongly adsorbing them so as to remove the effects of water and by-products caused by water in the organic electrolyte.
도 1은 종래의 방법에 따라 제조된 유기전해질을 적용한 경우에 대한 포텐셜 대비 전류 그래프이다.1 is a potential versus current graph for the case of applying the organic electrolyte prepared according to the conventional method.
도 2는 본 발명의 방법에 따라 제올라이트를 첨가하여 제조된 유기전해질을 적용한 경우에 대한 포텐셜 대비 전류 그래프이다.Figure 2 is a potential versus current graph for the case of applying the organic electrolyte prepared by the addition of zeolite according to the method of the present invention.
상기한 목적을 달성하기 위하여 본 발명에서는 유기전해질 및 유기전해질 총량을 기준으로 하여 20 중량% 이하의 제올라이트를 포함하는 전기에너지 저장 장치를 제공한다.In order to achieve the above object, the present invention provides an electrical energy storage device including 20 wt% or less of zeolite based on the total amount of organic electrolyte and organic electrolyte.
더욱 바람직하게는, 상기 제올라이트의 첨가량을 상기 유기전해질 총량을 기준으로 할 때 0.1 내지 20 중량% 범위가 되도록 한다. 만약 제올라이트의 첨가량이 0.1 중량% 보다 적으면 이의 첨가에 따른 효과가 미미하며 이의 첨가량이 20 중량% 보다 많으면 전해질로서의 특성이 열화되므로 상기한 첨가량 범위로 하는 것이 바람직하다.More preferably, the addition amount of the zeolite is in the range of 0.1 to 20% by weight based on the total amount of the organic electrolyte. If the addition amount of the zeolite is less than 0.1% by weight, the effect of addition thereof is insignificant, and if the addition amount thereof is more than 20% by weight, the characteristics as the electrolyte are deteriorated, so it is preferable to set the above addition amount range.
상기 유기전해질로서는 비프로톤성 극성 용매가 용이하게 적용되며 구체적으로는 에틸렌 카보네이트(EC), 프로필렌 카보네이트(PC), 디에틸 카보네이트(DEC), 디메틸 카보네이트(DMC), 에틸 메틸 카보네이트(EMC),-카프로락톤(-BL) 등과 같은 알킬 카보네이트계 용매, 아세토나이트릴 등을 들 수 있다.As the organic electrolyte, an aprotic polar solvent is easily applied. Specifically, ethylene carbonate (EC), propylene carbonate (PC), diethyl carbonate (DEC), dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), Caprolactone ( Alkyl carbonate solvents such as -BL), acetonitrile and the like.
본 발명에서는 물 및 물의 부산물로 인한 영향을 제거하기 위하여 이들을 강하게 흡착할 수 있는 제올라이트를 적절한 양으로 첨가함으로써 물에 의한 부반응을 억제하고 나아가 장치의 품질을 향상시키도록 한 것이다.In the present invention, in order to remove the effects of water and by-products of water, a zeolite capable of strongly adsorbing them is added in an appropriate amount to suppress side reactions caused by water and further improve the quality of the apparatus.
이하, 본 발명을 더욱 상세히 설명하기로 한다.Hereinafter, the present invention will be described in more detail.
제올라이트는 알칼리 및 알칼리토금속의 규산알루미늄 수화물인 광물의 일반적인 명칭이다. 제올라이트의 화학 조성은 Na, K, Ca, Mg, Sr 또는 Ba을 양이온으로 소량 함유하는 함수규산염(hydrous aluminosilicates) 이며, 결정 구조상으로는 규산염 광물의 기본 단위의 하나인 (Si,Al)O4사면체의 모든 산소들이 또 다른 사면체에 의해서 공유되면서 3차원적으로 연결되는 망상규산염(tektosilicates) 광물 형태를 이룬다.Zeolite is a generic name for minerals that are aluminum silicate hydrates of alkali and alkaline earth metals. The chemical composition of zeolite is hydrous aluminosilicates containing a small amount of Na, K, Ca, Mg, Sr or Ba as cation, and the crystal structure of (Si, Al) O 4 tetrahedron is one of the basic units of silicate mineral. All oxygen is shared by another tetrahedron, forming a three-dimensional linked tektosilicates mineral.
이러한 구조에서는 알루미늄 원자가 규소 원자에 비해서 전자의 개수가 하나 작기 때문에, 구조적으로 음전하를 가지게 되고, 그 자리에 양이온이 첨가되면서 결정 구조의 전하를 중성으로 만들어 주게 되므로, 결정 내부에 국부적인 전하 불균형으로 인해서 산성을 띠는 부분이나 염기성을 띠는 부분이 존재하며, 결정 내부에 일정한 크기를 가지면서 빈 공간을 존재하기 때문에 현재 촉매나 분자체, 탈수 및 재흡수 용도로 많이 사용되고 있다.In this structure, since aluminum atoms have a smaller number of electrons than silicon atoms, they have a structurally negative charge, and as a cation is added to their place, the charge of the crystal structure is neutralized, resulting in local charge imbalance within the crystal. Due to this, there is an acidic part or a basic part, and since it has a certain size and an empty space inside the crystal, it is widely used for catalysts, molecular sieves, dehydration and resorption.
제올라이트는 규산염 광물이므로 화학적으로 매우 안정하며, 전기가 통하지 않는 부도체이다. 그리고, 내부에 산점 및 염기점의 존재로 인해서, 물과 물에서 기인한 전하를 가지는 부산물의 흡착이 용이하므로, 물의 존재가 성능에 영향을 미치는 전기이중층 캐패시터나 이차전지와 같은 유기전해질을 사용하는 에너지 자장 기기의 경우, 제올라이트를 전해액에 첨가하여 물 및 물에 의한 부산물을 제올라이트에 흡착시킴으로써 그로 인한 부반응 및 기체의 발생을 줄일 수 있다.Since zeolite is a silicate mineral, it is chemically very stable and nonconductive insulator. In addition, due to the presence of acid and base points therein, the adsorption of water and by-products having a charge due to the water is easy, so that an organic electrolyte such as an electric double layer capacitor or a secondary battery in which the presence of water affects performance is used. In the case of an energy magnetic field device, zeolite may be added to the electrolyte to adsorb water and by-products by water to the zeolite, thereby reducing side reactions and gas generation.
특히 물을 흡착하면 300℃ 이상의 고온이 되어야 다시 탈착될 정도로 강한 화학적 흡착을 하기 때문에 흡착 이후에 흡착물이 상당히 안정한 상태를 유지할 수 있고, 규산염 광물의 특성상 화학적으로 매우 안정하며, 부도체이므로 사용중에 다른 영향을 미치지 않는다.In particular, when the water is adsorbed, the chemicals are strong enough to be desorbed only when the temperature is higher than 300 ° C, so that the adsorbate can be kept fairly stable after adsorption. Does not affect
특히, 제올라이트는 현재 1 마이크로미터 이하의 작은 입상으로 제조되는 경우가 많은데, 이렇게 미세한 입상으로 적용하면 전해액 내에 첨가하여 전극 표면까지 도달하게 하는 것이 매우 용이하다.In particular, zeolites are currently produced in small granules of 1 micrometer or less, and when applied in such fine granules, it is very easy to add them into the electrolyte and reach the electrode surface.
이하, 본 발명을 구체적인 실시예를 통하여 상세히 설명하기로 한다.Hereinafter, the present invention will be described in detail through specific examples.
<실시예 1><Example 1>
아세토나이트릴에 테트라에틸암모늄 테트라플루오르보레이트(TEABF4)를 용해시킨 전해액을 사용하는 경우, 전해액에 미립상의 제올라이트를 첨가함으로써 물에 의한 부반응이 억제되는 실험을 다음과 같이 수행하였다. 제올라이트의 첨가량은 질량비로 유기전해질의 10% 가 되게 첨가하였으며, 첨가한 제올라이트의 평균 입자 크기는 1㎛ 정도였다.When using an electrolyte solution in which tetraethylammonium tetrafluoroborate (TEABF 4 ) was dissolved in acetonitrile, an experiment in which side reaction by water was suppressed by adding fine zeolite to the electrolyte solution was performed as follows. The amount of zeolite added was 10% of the organic electrolyte by mass ratio, and the average particle size of the added zeolite was about 1 μm.
크기를 2cm x 3cm 로 한 탄소전극 (집전체는 20㎛의 알루미늄으로 하고 전극에서 탄소 부분의 두께는 160㎛, 탄소부분의 질량은 60㎎ 임)을 1M TEABF4/아세토나이트릴 전해액 내에서 실험하였다. 3전극법으로 실험하였으며 기준 전극으로는 Ag/AgClO4를 사용하였으며, 전위는 리튬 금속을 기준으로 환산하여 표현하였다.A carbon electrode with a size of 2 cm x 3 cm (the current collector is made of aluminum of 20 μm, the thickness of the carbon part of the electrode is 160 μm, and the mass of the carbon part is 60 mg) was tested in 1M TEABF 4 / acetonitrile electrolyte. It was. The experiment was conducted by a three-electrode method. Ag / AgClO 4 was used as a reference electrode, and the potential was expressed in terms of lithium metal.
실험은 선형 스윕 볼탐메트리(linear sweep voltammetry) 방법을 사용하여 0.2mV/초의 스캐닝 속도(scan rate)로 1.8V vs. Li부터 4.4V vs. Li 까지 전압을 이동시키면서 전류를 측정하였고, 각각 두 번에 걸쳐서 전압을 이동하여서 전류를 측정하였다. 사용한 장비는 EG & G 사의 Potentiostat/Galvanostat 273A를 사용하였다.Experiments were performed using a linear sweep voltammetry method with a scan rate of 0.2 mV / sec. 4.4V vs. Li The current was measured while moving the voltage to Li, and the current was measured by moving the voltage twice each. The equipment used was Potentiostat / Galvanostat 273A from EG & G.
<비교예 1>Comparative Example 1
비교를 위하여 실시예 1과 동일하게 수행하되 제올라이트를 첨가하지 않은유기전해질을 사용하고 동일한 방식으로 두 번에 걸쳐서 전압을 이동하면서 전류를 측정하였다.For comparison, the current was measured in the same manner as in Example 1 but using an organic electrolyte without addition of zeolite and moving the voltage twice in the same manner.
도 1은 제올라이트를 첨가하지 않은 비교예 1의 경우에 대한 결과를 나타내는 그래프로서 a는 첫 번째 스캐닝 결과이고, b는 두 번째 스캐팅 결과이다. 도 2는 제올라이트를 첨가한 실시예 1의 경우에 대한 결과를 나타내는 그래프로서 c는 첫 번째 스캐닝 결과이고, d는 두 번째 스캐닝 결과이다.1 is a graph showing the results for the case of Comparative Example 1 without adding zeolite, where a is the first scanning result and b is the second scattering result. Figure 2 is a graph showing the results for the case of Example 1 with added zeolite, c is the first scanning result, d is the second scanning result.
도 1에서 관찰할 수 있는 것은 스캐닝을 두 번 행하였을 때, 2.0V vs. Li 근방에서 일어나는 반응이 계속해서 발생하고 그 때의 반응에 의한 전류가 상당히 큰데 반하여 도 2에서는 2.0V vs. Li에서 일어나는 반응의 전류가 작으며 첫 번째 스캐닝에서만 피크가 나타나고 두 번째 스캐닝에서는 피크가 발생하지 않는다는 것을 확인할 수 있다.What can be observed in FIG. 1 is 2.0 V vs. when scanning is performed twice. The reaction occurring near Li continues to occur and the current caused by the reaction at that time is quite large, whereas in FIG. It can be seen that the current of the reaction in Li is small and peaks only in the first scan and no peak in the second scan.
2.0V vs. Li 에서는 일반적으로 물의 환원 반응이 발생하여 그에 의한 부산물로 OH-가 생성되고 또한 OH-존재시 이 전위 부근에서 다른 환원 반응이 일어난다고 알려져 있는데, 제올라이트를 첨가하는 경우, 수분 제거 및 OH-제거가 가능하게 되어서 부반응이 상당히 작아지는 것을 위의 실험을 통해서 확인할 수 있다. 따라서 전기이중층 캐패시터에 제올라이트를 첨가하는 것은 전해액 내의 물에 의한 부반응을 억제하는데 큰 효과가 있음을 확인할 수 있다.2.0V vs. Is generated and also OH - - In Li general, in the water reduction reaction occurs OH as a by-product of it there exist at the other reduction reaction in the vicinity of potential takes place and is known, in the case of the addition of zeolite, water removal and OH - to remove the It can be seen from the above experiment that the side reactions become quite small. Therefore, it can be confirmed that adding zeolite to the electric double layer capacitor has a great effect in suppressing side reactions caused by water in the electrolyte.
이상과 같은 본 발명에 의하면 물의 존재가 성능에 영향을 미치는 전기이중층 캐패시터나 이차전지와 같은 유기전해질을 사용하는 에너지 저장 장치의 경우, 제올라이트를 전해액 내에 첨가하는 것에 의해 물 및 물에 의한 부산물을 흡착시킴으로써 이로 인한 부반응 및 기체의 발생을 줄일 수 있게 된다.According to the present invention described above, in the case of an energy storage device using an organic electrolyte such as an electric double layer capacitor or a secondary battery in which the presence of water affects performance, water and water by-products are adsorbed by adding zeolite into the electrolyte. This can reduce side reactions and gas generation.
이상에서는 본 발명의 실시예에 따라 본 발명이 설명되었지만, 본 발명의 사상을 일탈하지 않는 범위 내에서 다양한 변형이 가능함은 본 발명이 속하는 기술 분야의 당업자라면 명확히 인지할 수 있을 것이다.Although the present invention has been described above according to an embodiment of the present invention, it will be apparent to those skilled in the art that various modifications may be made without departing from the spirit of the present invention.
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| WO2007049853A1 (en) * | 2005-10-26 | 2007-05-03 | Lg Chem, Ltd. | Secondary battery of improved life characteristics by elimination of metal ions |
| US20130224571A1 (en) * | 2010-12-13 | 2013-08-29 | Nec Corporation | Lithium ion secondary battery and method for manufacturing the same |
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| US7560191B2 (en) | 2005-10-26 | 2009-07-14 | Lg Chem, Ltd. | Secondary battery of improved life characteristics by elimination of metal ions |
| US20130224571A1 (en) * | 2010-12-13 | 2013-08-29 | Nec Corporation | Lithium ion secondary battery and method for manufacturing the same |
| DE102017217654A1 (en) | 2017-10-05 | 2019-04-11 | Robert Bosch Gmbh | Electrochemical cell comprising at least one molecular sieve |
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