KR100592112B1 - Electrode for Electric Double Layer Capacitor Fabricated Using Sulfonated Poly 2,6-dimethyl-1,4-phenylene Oxide - Google Patents
Electrode for Electric Double Layer Capacitor Fabricated Using Sulfonated Poly 2,6-dimethyl-1,4-phenylene Oxide Download PDFInfo
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- KR100592112B1 KR100592112B1 KR1020040050811A KR20040050811A KR100592112B1 KR 100592112 B1 KR100592112 B1 KR 100592112B1 KR 1020040050811 A KR1020040050811 A KR 1020040050811A KR 20040050811 A KR20040050811 A KR 20040050811A KR 100592112 B1 KR100592112 B1 KR 100592112B1
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- 239000003990 capacitor Substances 0.000 title claims abstract description 39
- -1 Poly 2,6-dimethyl-1,4-phenylene Polymers 0.000 title claims abstract description 16
- GVLZQVREHWQBJN-UHFFFAOYSA-N 3,5-dimethyl-7-oxabicyclo[2.2.1]hepta-1,3,5-triene Chemical compound CC1=C(O2)C(C)=CC2=C1 GVLZQVREHWQBJN-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 239000011230 binding agent Substances 0.000 claims abstract description 76
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 36
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 21
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229920002678 cellulose Polymers 0.000 claims abstract description 17
- 239000001913 cellulose Substances 0.000 claims abstract description 17
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 17
- 239000011737 fluorine Substances 0.000 claims abstract description 17
- 239000006258 conductive agent Substances 0.000 claims abstract description 16
- 239000003960 organic solvent Substances 0.000 claims abstract description 15
- 125000000542 sulfonic acid group Chemical group 0.000 claims abstract description 15
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 8
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical group C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 8
- 239000002033 PVDF binder Substances 0.000 claims description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 2
- 238000000576 coating method Methods 0.000 abstract description 8
- 239000011248 coating agent Substances 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 3
- 229920002852 poly(2,6-dimethyl-1,4-phenylene oxide) polymer Polymers 0.000 abstract 1
- 239000002002 slurry Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 239000011888 foil Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 3
- OKTJSMMVPCPJKN-YPZZEJLDSA-N carbon-10 atom Chemical compound [10C] OKTJSMMVPCPJKN-YPZZEJLDSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- OMIHGPLIXGGMJB-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]hepta-1,3,5-triene Chemical compound C1=CC=C2OC2=C1 OMIHGPLIXGGMJB-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 239000006245 Carbon black Super-P Substances 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229920001690 polydopamine Polymers 0.000 description 1
- 229940098458 powder spray Drugs 0.000 description 1
- YGSFNCRAZOCNDJ-UHFFFAOYSA-N propan-2-one Chemical compound CC(C)=O.CC(C)=O YGSFNCRAZOCNDJ-UHFFFAOYSA-N 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/38—Carbon pastes or blends; Binders or additives therein
-
- 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
Abstract
본 발명은 술폰화 폴리 2,6-디메틸-1,4-페닐렌 옥사이드를 이용하여 제작된 전기 이중층 캐패시터용 전극에 관한 것으로, 종래의 셀롤로오스계, 부타디엔계 및 불소계 결합제와 더불어 술폰산기를 포함한 결합제인 술폰화 폴리 2,6-디메틸-1,4-페닐렌 옥사이드를 유기 용매에 분산시킨 후 활성 탄소 분말과 도전제를 혼합하여 집전체에 도포함으로써 전극 도포 성능 및 전극 밀도를 증가하면서도 전극의 저항은 감소되고, 방전 특성을 향상된 전기 이중층 캐패시터용 전극 및 이를 이용한 전기 이중층 캐패시터를 제공하는 뛰어난 효과가 있다.The present invention relates to an electrode for an electric double layer capacitor fabricated using sulfonated poly 2,6-dimethyl-1,4-phenylene oxide, comprising a sulfonic acid group in addition to conventional cellulose, butadiene and fluorine-based binders. After dispersing the sulfonated poly 2,6-dimethyl-1,4-phenylene oxide as a binder in an organic solvent, the active carbon powder and the conductive agent are mixed and applied to the current collector to increase electrode coating performance and electrode density. The resistance is reduced and there is an excellent effect of providing an electrode for an electric double layer capacitor with improved discharge characteristics and an electric double layer capacitor using the same.
전기 이중층 캐패시터, 전기 이중층 캐패시터용 전극, EDLC, EDLC 전극, 술폰화 폴리(2,6-디메틸-1,4-페닐렌 옥사이드), SPPO Electric double layer capacitor, electrode for electric double layer capacitor, EDLC, EDLC electrode, sulfonated poly (2,6-dimethyl-1,4-phenylene oxide), SPPO
Description
도 1은 전기 이중층 캐패시터의 전하 저장 원리를 간략하게 나타낸 도면이다.1 is a schematic diagram illustrating the charge storage principle of an electric double layer capacitor.
도 2는 전기 이중층 캐패시터의 전극을 제조하기 위해 슬러리 제조 및 전극을 도포하는 공정의 흐름도이다.2 is a flow chart of a slurry preparation and process of applying an electrode to produce an electrode of an electric double layer capacitor.
도 3은 전기 이중층 캐패시터를 제조하는 공정도이다.3 is a process diagram for manufacturing an electric double layer capacitor.
삭제delete
본 발명은 술폰화 폴리 2,6-디메틸-1,4-페닐렌 옥사이드를 이용하여 제작된 전기 이중층 캐패시터용 전극에 관한 것으로, 더욱 상세하게는 술폰화 폴리 2,6-디메틸-1,4-페닐렌 옥사이드가 기존 결합제들과 함께 사용됨으로써 전극 밀도는 증가되고 방전 특성은 향상되면서 전극 저항은 감소되도록 제작된 전기 이중층 캐패시터용 전극에 관한 것이다.The present invention relates to an electrode for an electric double layer capacitor fabricated using sulfonated poly 2,6-dimethyl-1,4-phenylene oxide, and more particularly to sulfonated poly 2,6-dimethyl-1,4- The use of phenylene oxide in combination with existing binders relates to an electrode for an electric double layer capacitor that is designed to increase electrode density and improve discharge characteristics while reducing electrode resistance.
전기 이중층 캐패시터(Electric Double Layer Capacitor, EDLC)는 전극과 전해질간의 계면에서 발생되는 전기 이중층에 전하를 흡,탈착하는 원리를 이용하여 전기에너지를 축적하는 축전기이다(도 1 참고). 이러한 원리에 기인하여 전기 이중층 캐패시터는 빠른 충,방전 특성을 가지며, 높은 파워를 요구하는 이동용 정보 통신 기기인 핸드폰, 노트북, PDA 등의 보조 전원으로 뿐만 아니라 고용량을 요구하는 전기 자동차, 야간 도로 표시등, 그리고 UPS 등의 주전원 혹은 보조 전원으로 매우 적합하다.An electric double layer capacitor (EDLC) is a capacitor that accumulates electric energy by using a principle of absorbing and desorbing electric charges on an electric double layer generated at an interface between an electrode and an electrolyte (see FIG. 1). Due to this principle, the electric double layer capacitor has fast charging and discharging characteristics and is not only used as an auxiliary power source for mobile information communication devices such as mobile phones, laptops and PDAs, which require high power, but also for electric vehicles and night road lights. It is also very suitable for main or auxiliary power supply such as UPS.
이러한 다양한 용도를 가지는 전기 이중층 캐패시터의 전극은 넓은 비표면적을 통한 고 에너지화, 낮은 비저항을 통한 고 파워화, 그리고 계면에서의 전기화학 반응의 억제를 통한 전기화학적 안정성을 가지는 것이 중요한 과제이다.The electrodes of the electric double layer capacitor having such various uses have high energy through large specific surface area, high power through low specific resistance, and electrochemical stability through suppression of electrochemical reaction at the interface.
따라서 현재 넓은 비표면적을 가지는 활성탄소 분말(Activated Carbon Powder) 혹은 활성탄소 섬유(Activated Carbon Fiber)가 전극의 주재료로 가장 널리 이용되고 있으며, 이에 도전제를 혼합하거나, 혹은 금속 가루의 분사코팅 방식을 이용하여 낮은 비저항을 구현하고 있다. Therefore, activated carbon powder or activated carbon fiber, which has a large specific surface area, is currently widely used as a main material of an electrode, and a conductive agent or metal powder spray coating method is used. Low specific resistance.
또한 다양한 방법을 통하여 전극 계면에서 발생하는 전기화학적 부반응을 억제하여 보다 안정한 전극 물질을 연구, 개발 혹은 생산하고 있다.In addition, research and development or production of a more stable electrode material by suppressing the electrochemical side reactions occurring at the electrode interface through various methods.
상기와 같이 전기 이중층 캐패시터의 전극 활물질은 넓은 비표면적을 가지는 활성탄소 분말을 이용하는데, 이를 알루미늄(Aluminum) 집전체 위에 도포하기 위하여, 셀롤로오스(Cellulose)계, 부타디엔계, 혹은 불소계 (Fluoride)의 결합제를 유기 용매 혹은 물에 분산시켜 활성 탄소 분말과 혼합하여 슬러리(Slurry)화 혹은 페 이스트(Paste)화 하여, 수십에서 수백 um의 두께로 도포하여 사용하고 있다.As described above, the electrode active material of the electric double layer capacitor uses an activated carbon powder having a large specific surface area. In order to apply it on an aluminum current collector, a cellulose, butadiene, or fluoride system is used. The binder is dispersed in an organic solvent or water, mixed with activated carbon powder, slurryed or pasted, and applied to a thickness of several tens to hundreds of um.
그러나, 이러한 종래의 슬러리 제조 방법을 통한 전극 도포 공정에 사용되는 결합제의 경우 전기적으로 부도체이기 때문에 적정량 이상 함유시 전극 밀도는 증가 시킬 수 있으나, 전극 저항을 증가 시키거나 방전 특성을 저하시키는 요인으로 작용할 수 있다. However, since the binder used in the electrode coating process through the conventional slurry production method is an electrically nonconductive, the electrode density can be increased when contained in an appropriate amount or more, but it may act as a factor to increase the electrode resistance or lower the discharge characteristics. Can be.
따라서, 전극 제조시 결합제 비율은 15중량% 이내로 결정해야만 전극의 표면 저항 및 제품의 저항 특성을 기준치내로 유지할 수 있는 단점을 가지고 있다.Therefore, the binder ratio in manufacturing the electrode has a disadvantage that the surface resistance of the electrode and the resistance characteristics of the product can be maintained within the reference value only within 15% by weight.
또한, 결합제 비율의 제한은 전극 밀도를 향상시키는데 있어, 특정치 이상으로의 증진을 불가능하게 하는 요인으로 작용하고 있다.In addition, the limitation of the binder ratio serves as a factor in making it impossible to improve above a certain value in improving the electrode density.
이에 본 발명자들은 상기 단점을 고려하여 종래의 셀롤로오스계, 부타디엔계, 그리고 불소계 결합제가 과량 사용시 전극 저항이 증가하고 제품의 방전 특성이 저하되는 단점을 해결하기 위하여 술폰산기를 포함하는 결합제를 기존 결합제들과 혼합 사용함으로써 전극 도포 성능 및 전극 밀도는 증가시키면서도 전극의 저항을 감소시키고 방전 특성은 향상 시킨 전극을 제조하고 상기 전극을 이용하여 전기 이중층 캐패시터를 제조함으로써 본 발명을 완성하였다.In view of the above disadvantages, the inventors of the present invention provide a conventional binder containing a sulfonic acid group in order to solve the disadvantage that the conventional cellulose-based, butadiene-based, and fluorine-based binders have excessive electrode resistance and deteriorate discharge characteristics of products. The present invention was completed by manufacturing an electrode having reduced electrode resistance and improved discharge characteristics while increasing electrode coating performance and electrode density by using a mixture thereof, and manufacturing an electric double layer capacitor using the electrode.
따라서, 본 발명의 목적은 셀룰로오스계 결합제, 불소계 결합제 및 부타디엔계 결합제를 유기 용매에 분산시킨 후 활성 탄소 분말과 도전제를 혼합하여 집전체에 도포하여 제작된 전기 이중층 캐패시터용 전극에 있어서, 상기 결합제들과 더불어 술폰산기를 포함하는 결합제를 추가로 혼합하여 제작되는 것을 특징으로 하는 전기 이중층 캐패시터용 전극을 제공하는데 있다.Accordingly, an object of the present invention is to disperse a cellulose-based binder, a fluorine-based binder and a butadiene-based binder in an organic solvent, and then to mix an activated carbon powder and a conductive agent and apply an electrical current to an electrical current collector. In addition to the present invention is to provide an electrode for an electric double layer capacitor, characterized in that additionally produced by mixing a binder containing a sulfonic acid group.
본 발명의 또 다른 목적은 셀룰로오스계 결합제, 불소계 결합제 및 부타디엔계 결합제를 유기 용매에 분산시킨 후 활성 탄소 분말과 도전제를 혼합하여 집전체에 도포하여 제작된 전기 이중층 캐패시터용 전극에 있어서, 상기 결합제들과 더불어 술폰산기를 포함하는 결합제를 추가로 혼합하여 제작된 전기 이중층 캐패시터용 전극을 이용하여 제작되는 것을 특징으로 하는 전기 이중층 캐패시터를 제공하는데 있다.Another object of the present invention is an electrode for an electric double layer capacitor prepared by dispersing a cellulose binder, a fluorine binder and a butadiene binder in an organic solvent, and then applying an active carbon powder and a conductive agent to a current collector. In addition to the present invention to provide an electric double layer capacitor, characterized in that it is manufactured using an electrode for an electric double layer capacitor prepared by further mixing a binder containing a sulfonic acid group.
본 발명의 상기 목적은 종래의 셀롤로오스계, 부타디엔계 및 불소계 결합제와 더불어 술폰산기를 포함한 결합제를 혼합 사용함으로써, 전극 도포 성능 및 전극 밀도를 증가시키면서도 전극의 저항을 감소시키고, 방전 특성을 향상 시켜, 전극 밀도는 10% 이상, 방전 특성은 10% 이상 증가 시킬 수 있으며, 전극 저항은 20% 이상 감소 시킬 수 있는 전기 이중층 캐패시터용 전극 및 이를 이용한 전기 이중층 캐패시터를 제조함으로써 달성하였다.
The object of the present invention is to mix the conventional cellulose-based, butadiene-based and fluorine-based binders with a binder containing a sulfonic acid group, thereby increasing the electrode coating performance and electrode density while reducing the electrode resistance and improving the discharge characteristics The electrode density can be increased by more than 10%, the discharge characteristics can be increased by more than 10%, and the electrode resistance can be achieved by manufacturing an electrode for an electric double layer capacitor and an electric double layer capacitor using the same can be reduced by more than 20%.
이하 본 발명의 구성을 설명한다.Hereinafter, the configuration of the present invention.
본 발명에서는 셀룰로오스계 결합제, 불소계 결합제 및 부타디엔계 결합제를 유기 용매에 분산시킨 후 활성 탄소 분말과 도전제를 혼합한 후 집전체에 도포하여 제작된 전기 이중층 캐패시터용 전극에 있어서, 상기 결합제들과 함께 술폰산기를 포함하는 결합제를 추가 혼합하여 제작되는 것을 특징으로 하는 전기 이중층 캐패시터용 전극을 제공한다.In the present invention, a cellulosic binder, a fluorine-based binder and a butadiene-based binder is dispersed in an organic solvent, and then the active carbon powder and the conductive agent are mixed, and then applied to a current collector. The present invention provides an electrode for an electric double layer capacitor, which is prepared by further mixing a binder including a sulfonic acid group.
본 발명에서 상기 술폰산기를 포함하는 결합제의 바람직한 예로는 하기 화학식 1의 술폰화 폴리 2,6-디메틸-1,4-페닐렌 옥사이드를 들 수 있다.
본 발명에서, 상기 유기 용매는 이소프로필 알코올, N-메틸피롤리돈 및 아세톤으로 구성되는 그룹 중에서 선택되는 어느 하나 이상인 것이 바람직하다. In the present invention, the organic solvent is preferably any one or more selected from the group consisting of isopropyl alcohol, N-methylpyrrolidone and acetone.
본 발명에서 유기 용매는 결합제를 분산시키기 위한 매개체로 사용되었으며 선택되는 결합제에 따라 잘 분산되는 유기 용매로 선택하여 사용할 수 있으며 유기 용매의 양은 본 발명에서 제작하는 전극의 특성에 아무런 영향을 주지 못한다.In the present invention, the organic solvent is used as a medium for dispersing the binder and can be selected and used as an organic solvent that is well dispersed according to the binder selected. The amount of the organic solvent does not affect the characteristics of the electrode manufactured in the present invention.
본 발명에서 상기 활성 탄소 분말: 도전제: 술폰산기를 포함하는 결합제, 셀룰로오스계 결합제, 불소계 결합제 및 부타디엔계 결합제를 포함하는 결합제의 혼합 비율은 70∼80 중량부: 5∼20 중량부: 5∼20 중량부인 것이 바람직하다. 상기 성분 중 도전제의 혼합비율은 제조하고자 하는 전극의 특성 즉, 전극 밀도, 방전 특성 또는 전극 저항에 크게 영향을 미치지 않는다. 다만, 도전제가 5∼20 중량부일 때 본 발명에서 이루고자 하는 효과가 가장 바람직하였다. 즉, 전극 밀도 및 방전 특성은 10% 이상 증가시키고 전극 저항은 20% 이상 감소시킬 수 있다. In the present invention, the mixing ratio of the activated carbon powder: conductive agent: a binder containing a sulfonic acid group, a cellulose-based binder, a fluorine-based binder and a butadiene-based binder is 70 to 80 parts by weight: 5 to 20 parts by weight: 5 to 20 parts by weight. It is preferable that it is a weight part. The mixing ratio of the conductive agent in the above components does not significantly affect the characteristics of the electrode to be manufactured, that is, the electrode density, the discharge characteristics or the electrode resistance. However, the effect to achieve in the present invention was most preferred when the conductive agent is 5 to 20 parts by weight. That is, the electrode density and discharge characteristics can be increased by 10% or more and the electrode resistance can be reduced by 20% or more.
삭제delete
한편, 상기 성분 중 본 발명의 전극 특성에 가장 큰 영향을 미치는 성분은 결합제로서 결합제가 5 중량부보다 적게 사용되면 전극의 저항은 감소하지만 활성 탄소가 도전제와 혼합되어 집전제에 도포될 수 있을 만큼 응겨붙지 못하며 20 중량부보다 많이 사용되는 경우에는 활성 탄소와 도전제가 집전제에 잘 도포되지만 전극의 저항은 증가하는 단점을 가진다.On the other hand, the component that most affects the electrode properties of the present invention of the above components are used as a binder less than 5 parts by weight of the electrode resistance is reduced but activated carbon may be mixed with the conductive agent and applied to the current collector When it is not coagulated as much as 20 parts by weight is used, the active carbon and the conductive agent is well applied to the current collector, but the resistance of the electrode has the disadvantage that increases.
그리고, 상기 성분 중 활성 탄소 분말의 혼합비율을 달리하여 전극을 제조하고 전극 밀도, 방전 특성 및 전극 저항을 측정하면 활성 탄소 분말의 혼합 비율이 70∼80 중량부일 때 가장 바람직한 값을 나타냄을 알 수 있다.In addition, when the electrode was manufactured by varying the mixing ratio of the activated carbon powder among the components, and the electrode density, the discharge characteristics, and the electrode resistance were measured, it was found that the most preferable value was obtained when the mixing ratio of the activated carbon powder was 70 to 80 parts by weight. have.
아울러, 본 발명에서 셀룰로오스계 결합제, 불소계 결합제 및 부타디엔계 결합제를 혼합하여 함께 사용한 것은 다양한 결합제를 섞어 사용함에 따라 활물질 즉, 활성 탄소 분말이 서로 잘 붙어 집전체에 도포되는 능력이 크기 때문으로 본 발명자에 의하여 발명되어 2003년 5월 1일자로 특허출원된 대한민국 특허출원 제 2003-0027968호에 기재된 바와 같다.In addition, in the present invention, the cellulose-based binder, the fluorine-based binder, and the butadiene-based binder are mixed and used together because the active material, that is, the activated carbon powder adheres well to each other and is applied to the current collector as the various binders are mixed and used. It is as described in the Republic of Korea Patent Application No. 2003-0027968, which was invented by the patent application dated May 1, 2003.
본 발명에서 상기 결합제들의 혼합 비율은 술폰산기를 포함하는 결합제: 셀룰로오스계 결합제: 불소계 결합제: 부타디엔계 결합제가 5∼10 중량부: 1∼8 중량부: 1∼7 중량부: 1∼7 중량부인 것이 바람직하다. 상기와 같은 혼합 비율에서 가장 바람직한 전극 특성을 가진다. 즉, 전극 밀도 및 방전 특성은 10% 이상 증가하고 전극 저항은 20% 이상 감소시킬 수 있다. 술폰산기를 포함하는 결합제가 5 중량부보다 적으면 전극 저항은 커지며 술폰산기를 포함하는 결합제가 10 중량부보다 많으면 다른 결합제의 양이 상대적으로 적어 다양한 결합제들간의 상승작용으로 인한 활성 탄소 분말의 응집력이 약하여 집전체에 도포되기 어려워지는 단점이 있다.In the present invention, the mixing ratio of the binder is a binder containing a sulfonic acid group: cellulose-based binder: fluorine-based binder: butadiene-based binder is 5 to 10 parts by weight: 1 to 8 parts by weight: 1 to 7 parts by weight: 1 to 7 parts by weight. desirable. It has the most desirable electrode properties at such mixing ratios. That is, the electrode density and discharge characteristics can be increased by 10% or more and the electrode resistance can be reduced by 20% or more. If the binder containing sulfonic acid group is less than 5 parts by weight, the electrode resistance is high. If the binder containing sulfonic acid group is more than 10 parts by weight, the amount of the other binder is relatively small, so that the cohesive force of the activated carbon powder due to synergy between various binders is weak. There is a disadvantage in that it is difficult to apply to the current collector.
본 발명은 상기 전극들을 이용하여 제작된 전기 이중층 캐패시터를 제공한다.The present invention provides an electric double layer capacitor fabricated using the electrodes.
본 발명의 전기 이중층 캐패시터용 전극은 술폰산기를 포함하는 결합제, 셀룰로오스계 결합제, 불소계 결합제, 그리고 부타디엔계 결합제들을 유기 용매에 분산시킨 후, 활성탄소 분말과 도전제를 혼합하여 집전체인 알루미늄 포일 상에 도포하여 제작된다(도 2 참고).The electrode for an electric double layer capacitor of the present invention is a binder containing a sulfonic acid group, a cellulose-based binder, a fluorine-based binder, and butadiene-based binders are dispersed in an organic solvent, and then mixed with an activated carbon powder and a conductive agent on an aluminum foil as a current collector. It is produced by application (see Fig. 2).
본 발명에서 사용된 활성탄소 분말은 비표면적이 1500∼2500 ㎡/g이고, 평균 입경이 5∼15 ㎛이며, 벌크 밀도가 0.30∼0.50 g/mL 이고, pH가 6.0∼7.0 인 것을 사용한다.The activated carbon powder used in the present invention has a specific surface area of 1500 to 2500 m 2 / g, an average particle diameter of 5 to 15 µm, a bulk density of 0.30 to 0.50 g / mL, and a pH of 6.0 to 7.0.
본 발명에서 사용된 도전제는 비표면적이 55∼65 ㎡/g이고, 평균 입경이 30∼50 nm 이며, pH가 9.0∼10.0 인 카본 블랙 계열의 것을 사용한다. 대표적인 예로는 슈퍼-피(Super-P)(MMM, USA)가 있다.The conductive agent used in the present invention uses a carbon black series having a specific surface area of 55 to 65 m 2 / g, an average particle diameter of 30 to 50 nm, and a pH of 9.0 to 10.0. A representative example is Super-P (MMM, USA).
본 발명에서 결합제를 분산시키는 유기 용매들의 대표적인 예는 이소프로필 알코올(IPA), N-메틸피롤리돈(NMP) 그리고 아세톤(Acetone) 등이다.Representative examples of the organic solvents for dispersing the binder in the present invention are isopropyl alcohol (IPA), N-methylpyrrolidone (NMP) and acetone (Acetone) and the like.
또한, 본 발명에서 사용된 결합제들의 대표적인 예로는 술폰산기를 포함한 결합제인 술폰화 폴리 2,6-디메틸-1,4-페닐렌 옥사이드(SPPO), 셀롤로오스계의 카르복시메틸셀룰로오스(CMC), 불소계의 폴리테트라플루오로에틸렌(PTFE), 폴리비닐리덴플루오라이드(PVdF) 및 부타디엔계의 부타디엔-스티렌(BS) 공중합체가 있다.In addition, representative examples of the binders used in the present invention are sulfonated poly 2,6-dimethyl-1,4-phenylene oxide (SPPO), a cellulose methyl carboxymethyl cellulose (CMC), a fluorine-based binder Polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVdF) and butadiene-based butadiene-styrene (BS) copolymers.
본 발명에 따르면 전극 도포 성능을 증가시키면서도 전극의 저항을 감소시키고, 방전 특성을 향상 시켜, 셀롤로오스계, 부타디엔계, 그리고 불소계 결합제만을 사용하여 제조된 전극에 비해, 전극 밀도는 10% 이상, 방전 특성은 10% 이상 증가 시킬 수 있으며, 저항은 20% 이상 감소시킬 수 있다.According to the present invention, while increasing the electrode coating performance while reducing the resistance of the electrode and improve the discharge characteristics, the electrode density is 10% or more, compared to the electrode manufactured using only cellulose, butadiene, and fluorine-based binders, The discharge characteristics can be increased by more than 10% and the resistance can be reduced by more than 20%.
이하, 본 발명을 실시예에 의해 상세히 설명하고자 하나, 하기 실시예는 본 발명을 예시하기 위한 것일 뿐 본 발명의 범위를 한정하는 것은 아니다.Hereinafter, the present invention will be described in detail by way of examples, but the following examples are only for illustrating the present invention and are not intended to limit the scope of the present invention.
실시예 1: 술폰화 폴리 2,6-디메틸-1,4-페닐렌 옥사이드를 이용하여 제조한 본 발명 전기 이중층 캐패시터용 전극의 제조Example 1 Preparation of Electrode for Electric Double Layer Capacitor of the Invention Prepared Using Sulfonated Poly 2,6-dimethyl-1,4-phenylene Oxide
유기 용매 N-메틸피롤리돈(NMP) 300g에 술폰화 폴리 2,6-디메틸-1,4-페닐렌 옥사이드(SPPO) 5g, 카르복시메틸셀롤로오스(CMC) 5g, 폴리비닐리덴플루오라이드(PVdF) 5g 및 부타디엔-스티렌(BS) 5g을 첨가하여 용해시켜서 결합제 용액을 제조하였다.300 g of organic solvent N-methylpyrrolidone (NMP), 5 g of sulfonated poly 2,6-dimethyl-1,4-phenylene oxide (SPPO), 5 g of carboxymethylcellulose (CMC), polyvinylidene fluoride ( A binder solution was prepared by dissolving 5 g of PVdF) and 5 g of butadiene-styrene (BS).
활성 탄소 분말 70g과 도전제 10g을 정량하여 혼합 용기에 담고 여기에 상기에서 제조한 결합제 용액을 넣은 후 6시간 동안 혼합하여 슬러리를 제조하였다. 슬러리의 점도는 약 2800cps 정도였다.70 g of the activated carbon powder and 10 g of the conductive agent were quantified and placed in a mixing vessel, and the binder solution prepared above was added thereto, followed by mixing for 6 hours to prepare a slurry. The viscosity of the slurry was about 2800 cps.
상기 슬러리를 콤마 다이렉트 롤(Comma Direct Roll) 방식의 도포기를 사용하여 도포 두께가 알루미늄 포일의 두께를 제외하고, 양면이 200um가 되도록 도포하였다.The slurry was applied using a comma direct roll type applicator so that the coating thickness was 200 μm except for the thickness of the aluminum foil.
도포가 완료된 전극은 롤프레스(Roll Press)기를 사용하여 두께가 알루미늄 포일의 두께를 제외하고 양면이 180um가 되도록 약 10%가량 가열 압착하였다.The coated electrode was heated and pressed by about 10% by using a roll press (Roll Press) so that the thickness is 180um on both sides except the thickness of the aluminum foil.
상기에서 제조된 전극의 경우 저항은 11.2 Ω㎠이며, 전극 밀도는 0.715 g/ ㎠를 나타내었다. In the case of the electrode prepared above, the resistance was 11.2 Ωcm 2 and the electrode density was 0.715 g / cm 2.
이렇게 제조된 전극을 이용하여 원통형 타입의 전기 이중층 캐패시터를 제조하여 등가 직렬 저항(Equvalent Series Resistance: ESR)을 측정한 결과 12 mΩ이었고, 정전 용량은 73.7 F가 구현되었다(도 3 참고).An electric double-layer capacitor of a cylindrical type was manufactured using the electrode thus prepared, and an equivalent series resistance (ESR) was measured. As a result, an electrostatic capacitance of 73.7 F was realized (see FIG. 3).
실시예 2: 술폰화 폴리 2,6-디메틸-1,4-페닐렌 옥사이드를 이용하여 제조한 본 발명 전기 이중층 캐패시터용 전극의 제조Example 2 Preparation of Electrode for Electric Double Layer Capacitor of the Invention Prepared Using Sulfonated Poly 2,6-dimethyl-1,4-phenylene Oxide
유기 용매 N-메틸피롤리돈(NMP) 300g에 술폰화 폴리 2,6-디메틸-1,4-페닐렌 옥사이드(SPPO) 10g, 카르복시메틸셀롤로오스(CMC) 3g, 폴리테트라플루오로에틸렌(PTFE) 3g 및 부타디엔-스티렌(BS) 4g을 첨가하여 용해시켜 결합제 용액을 제조하였다.300 g of organic solvent N-methylpyrrolidone (NMP), 10 g of sulfonated poly 2,6-dimethyl-1,4-phenylene oxide (SPPO), 3 g of carboxymethyl cellulose (CMC), polytetrafluoroethylene ( 3 g of PTFE) and 4 g of butadiene-styrene (BS) were added to dissolve to prepare a binder solution.
활성 탄소 분말 70g과 도전제 10g을 정량하여 혼합 용기에 담고 여기에 상기 결합제 용액을 넣은 후 6시간 동안 혼합하여 슬러리를 제조하였다. 슬러리의 점도는 약 2500cps 정도였다.70 g of activated carbon powder and 10 g of a conductive agent were quantified and placed in a mixing vessel, and the binder solution was added thereto, followed by mixing for 6 hours to prepare a slurry. The viscosity of the slurry was about 2500 cps.
상기 슬러리를 콤마 다이렉트 롤(Comma Direct Roll) 방식의 도포기를 사용하여 도포 두께가 알루미늄 포일의 두께를 제외하고, 양면이 200um가 되도록 도포하였다.The slurry was applied using a comma direct roll type applicator so that the coating thickness was 200 μm except for the thickness of the aluminum foil.
도포가 완료된 전극은 롤프레스(Roll Press)기를 사용하여 두께가 알루미늄 포일의 두께를 제외하고 양면이 180um가 되도록 약 10%가량 가열 압착하였다.The coated electrode was heated and pressed by about 10% by using a roll press (Roll Press) so that the thickness is 180um on both sides except the thickness of the aluminum foil.
상기에서 제조된 전극의 경우 저항은 약 10.4 Ω㎠이며, 전극 밀도는 0.737 g/㎠를 나타내었다. In the case of the electrode prepared above, the resistance was about 10.4 Ω cm 2 and the electrode density was 0.737 g / cm 2.
이렇게 제조된 전극을 이용하여 원통형 타입의 전기 이중층 캐패시터를 제조하여 등가 직렬 저항(Equvalent Series Resistance: ESR)을 측정한 결과 12 mΩ이었고, 정전 용량은 74.8 F가 구현되었다(도 3 참고).As a result of measuring an equivalent series resistance (ESR) of a cylindrical type electric double layer capacitor using the electrode thus prepared, it was 12 mΩ, and the capacitance was 74.8 F (see FIG. 3).
이상 상기에서 살펴본 바와 같이 본 발명 술폰화 폴리 2,6-디메틸-1,4-페닐렌 옥사이드를 이용하여 제작된 전기 이중층 캐패시터용 전극은 종래의 셀롤로오스계, 부타디엔계 및 불소계 결합제와 더불어 술폰산기를 포함한 결합제를 혼합 사용함으로써, 전극 도포 성능 및 전극 밀도를 증가시키면서도 전극의 저항을 감소시키고, 방전 특성을 향상 시켜, 전극 밀도는 10% 이상, 방전 특성은 10% 이상 증가 시킬 수 있으며, 전극 저항은 20% 이상 감소 시킬 수 있는 전기 이중층 캐패시터용 전극 및 이를 이용한 전기 이중층 캐패시터를 제공하는 뛰어난 효과가 있으므로 전기전자산업상 매우 유용한 것이다.As described above, the electrode for an electric double layer capacitor fabricated using the sulfonated poly 2,6-dimethyl-1,4-phenylene oxide of the present invention is a sulfonic acid in addition to conventional cellulose-based, butadiene-based and fluorine-based binders. By using a binder containing groups, the electrode resistance can be increased while increasing the electrode coating performance and electrode density, and the discharge characteristics can be improved. The electrode density can be increased by 10% or more and the discharge characteristic can be increased by 10% or more. Is very useful in the electrical and electronics industry because it has an excellent effect of providing an electrode for an electric double layer capacitor and an electric double layer capacitor using the same can be reduced by more than 20%.
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| JP2003017370A (en) | 2001-06-29 | 2003-01-17 | Masayuki Yoshio | Coating paste for capacitor and electric double layer capacitor electrode |
| KR200320683Y1 (en) | 2003-05-01 | 2003-07-22 | 주식회사 디지털텍 | Electric Double Layer Capacitors |
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| JP2003017370A (en) | 2001-06-29 | 2003-01-17 | Masayuki Yoshio | Coating paste for capacitor and electric double layer capacitor electrode |
| KR200320683Y1 (en) | 2003-05-01 | 2003-07-22 | 주식회사 디지털텍 | Electric Double Layer Capacitors |
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| WO2012008641A1 (en) * | 2010-07-13 | 2012-01-19 | 주식회사 네스캡 | Electrode for electrochemical capacitor and method for preparing same |
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