KR20090066881A - Preparation method of electrode for electric double-layer capacitor - Google Patents
Preparation method of electrode for electric double-layer capacitor Download PDFInfo
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- KR20090066881A KR20090066881A KR1020070134617A KR20070134617A KR20090066881A KR 20090066881 A KR20090066881 A KR 20090066881A KR 1020070134617 A KR1020070134617 A KR 1020070134617A KR 20070134617 A KR20070134617 A KR 20070134617A KR 20090066881 A KR20090066881 A KR 20090066881A
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- layer capacitor
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- electric double
- activated carbon
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- 239000003990 capacitor Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 80
- 239000007772 electrode material Substances 0.000 claims abstract description 32
- 238000004519 manufacturing process Methods 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000002253 acid Substances 0.000 claims abstract description 22
- 238000010438 heat treatment Methods 0.000 claims abstract description 19
- 239000012535 impurity Substances 0.000 claims abstract description 17
- 239000003513 alkali Substances 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 25
- 239000000243 solution Substances 0.000 claims description 25
- 239000012670 alkaline solution Substances 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 15
- 239000002994 raw material Substances 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 229920006395 saturated elastomer Polymers 0.000 claims description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 230000002829 reductive effect Effects 0.000 abstract description 3
- 238000012545 processing Methods 0.000 abstract description 2
- 239000002351 wastewater Substances 0.000 abstract description 2
- 238000001994 activation Methods 0.000 description 7
- 238000003860 storage Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 230000003213 activating effect Effects 0.000 description 6
- 230000004913 activation Effects 0.000 description 6
- 125000000524 functional group Chemical group 0.000 description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 235000013162 Cocos nucifera Nutrition 0.000 description 4
- 244000060011 Cocos nucifera Species 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000003245 coal Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- -1 nitric acid (HNO 3 ) Chemical class 0.000 description 4
- 239000005486 organic electrolyte Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000000809 air pollutant Substances 0.000 description 1
- 231100001243 air pollutant Toxicity 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 239000002894 chemical waste Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000002006 petroleum coke Substances 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000003716 rejuvenation Effects 0.000 description 1
- 239000011257 shell material Substances 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000003403 water pollutant Substances 0.000 description 1
- 239000002023 wood 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
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
-
- 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
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- 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
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Carbon And Carbon Compounds (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
Abstract
Description
본 발명은 전기이중층 캐패시터용 전극재의 제조방법에 관한 것으로, 보다 상세하게는 상용의 활성탄을 원료로 하여 알칼리용액으로 처리한 후 산용액으로 처리하고 세척하여 건조한 후 불활성분위기 또는 환원성분위기에서 열처리하는 방법에 의한 전기이중층 캐패시터용 전극재의 제조방법에 관한 것이다.The present invention relates to a method for manufacturing an electrode material for an electric double layer capacitor, and more particularly, a method of treating with an alkaline solution using commercially available activated carbon as a raw material, then treating with an acid solution, washing and drying, and then heat-treating in an inert or reducing atmosphere. The manufacturing method of the electrode material for electric double layer capacitors by this invention is related.
전기이중층 캐패시터는 전기자동차등에 사용되는 일종의 고용량 콘덴서로서 전기저장용량은 전극의 면적에 비례하는 특성을 가지므로 고용량화를 위하여 그 전극재료로서 일반의 콘덴서와는 다른 비표면적이 높고 전기전도도가 높은 활성탄류가 사용되고 있다. Electric double layer capacitor is a kind of high capacity capacitor used in electric vehicles, and because its electric storage capacity has the property proportional to the area of the electrode, it has high specific surface area and high electrical conductivity unlike other condensers. Is being used.
대한민국 특허 제85518호에는 활성탄소섬유를 전극으로 사용하는 전기이중층 캐패시터의 제조방법이 개시되어 있으며 특허출원 제1998-7009209호에는 전기이중층 캐패시터용의 미세공을 가진 탄소재료 전극재 제조방법을 개시하고 있다. 그 러나 일반적으로 활성탄소섬유의 세공은 20Å 이하의 미세공에 국한되는 특성을 가지고 있으므로 수산화칼륨등을 전해액으로 사용하는 수용액계 전기이중층 캐패시터의 용량은 유지되지만 중간세공이 요구되는 프로필렌카보네이트(Propylene carbonate) 등의 유기계 전해질을 사용하는 전기이중층 캐패시터에 사용하기에는 축전용량이 저하되는 특성을 가지고 있다. Korean Patent No. 85518 discloses a method of manufacturing an electric double layer capacitor using activated carbon fibers as an electrode, and Patent Application No. 1998-7009209 discloses a method of manufacturing a carbon material electrode material having fine pores for an electric double layer capacitor. have. However, in general, the pore of activated carbon fiber is limited to the fine pores of 20Å or less. Therefore, the capacity of aqueous double layer capacitor using potassium hydroxide as electrolyte is maintained, but propylene carbonate is required. It has a characteristic that the storage capacity is lowered for use in an electric double layer capacitor using an organic electrolyte such as).
이와 같은 단점을 해결하고자 본 발명자 등에 의한 대한민국 특허 제2003-95332호에는 금속을 포함하는 전기이중층 캐패시터 전극재를 제조하는 방법을 개시하고 있다. 이 방법은 기존의 방법에 비하여 축전용량이 증대되는 효과를 가지고 있으나 활성화과정에서 금속에 의한 촉매분해작용이 일어나서 표면에 산소함유관능기를 많이 포함하게 되어 이에 의하여 전기이중층 캐패시터로 작동시에 부수적인 화학반응을 나타내어 부풀게 하며 또한 충방전반복에 따른 용량의 저하를 일으키는 단점을 가지고 있었다.Korean Patent No. 2003-95332 by the inventors to solve the above disadvantages discloses a method of manufacturing an electric double layer capacitor electrode material containing a metal. This method has the effect of increasing the capacitance compared to the existing method, but the catalytic decomposition action by the metal occurs during the activation process, it contains a lot of oxygen-containing functional groups on the surface, thereby causing additional chemicals when operating as an electric double layer capacitor The reaction was inflated and had a disadvantage of causing a decrease in capacity due to repeated charge and discharge.
이와 같은 방법들은 충방전용량이 상대적으로 큰 특성을 가지고 있으므로 특수한 고용량용의 전극재로서 활용할 수는 있으나 처리에 필요한 화학약품이 매우 고가이며 또한 처리공정이 대용량화에는 한계가 있어 대량생산이 곤란한 단점을 가지고 있다. 따라서 대량 생산을 위한 일반적인 상업적 제조방법으로 가장 많이 사용되고 있는 방법은 원료로서 회분을 적게 함유하고 있는 석유계 및 석탄계의 코크스를 사용하여 수산화칼륨(KOH) 또는 수산화나트륨(NaOH) 등의 강알칼리와 혼합한 후 열처리하고 세척에 의하여 분리하는 화학적 활성화 방법에 의하여 제조되고 있다. 이 방법은 상대적으로 대량생산이 가능하며 전기이중층 캐패시터의 전극재로 사용하는데 있어서 비교적 우수한 성능을 나타내고 있으나 강알칼리성 활성화조제를 원료의 3~4배 이상 사용하게 되므로 대량의 활성화조제가 소모되므로 제조비용이 매우 높으며 열처리 후 첨가된 활성화조제를 세척공정에서 모두 용출시켜서 분리하게 되므로 대량의 강알칼리성 화학폐기물이 발생하게 되어 이의 처리에 추가적인 제조비용이 소요되므로 제조비용이 매우 높아 전기이중층 캐패시터의 제조비용에 있어서 전극재가 차지하는 비중이 가장 크게 되어 전기이중층 캐패시터의 우수한 전기적 특성에도 불구하고 이의 활용에 제한을 가지게 되는 문제점을 가지고 있다.These methods can be used as a special high capacity electrode material because they have relatively high charge and discharge capacity, but chemicals required for treatment are very expensive, and the processing process has a limitation in large capacity, which makes it difficult to mass-produce. Have. Therefore, the most commonly used method for general commercial production for mass production is to mix with strong alkali such as potassium hydroxide (KOH) or sodium hydroxide (NaOH) using petroleum and coal based coke containing less ash as raw material. It is prepared by a chemical activation method which is then heat treated and separated by washing. This method is relatively mass-producible and shows relatively good performance in using as an electrode material for electric double layer capacitors. However, since strong alkaline activating aids are used three to four times more than the raw materials, a large amount of activating aids are consumed, thus producing costs. This is very high, and since the activating aid added after the heat treatment is separated by eluting in the washing process, a large amount of strong alkaline chemical waste is generated, and additional manufacturing cost is required for the treatment thereof, so the manufacturing cost is very high and thus the manufacturing cost of the electric double layer capacitor is increased. In this case, the electrode material occupies the largest proportion, and thus has a problem in that its utilization is limited despite the excellent electrical characteristics of the electric double layer capacitor.
따라서, 본 발명은 이와 같은 점을 개선하고자 상대적으로 대량으로 입수가 가능한 출발물질을 이용하여 저가의 비용으로 대량으로 제조되는 상용의 활성탄을 원료로 하여 알칼리용액 및 산용액에서 불순물을 용출시킨 후 세척하여 건조한 후 불활성분위기 또는 환원성분위기에서 열처리하는 방법에 의하여 제조공정에 투입되는 활성화조제와 세척에 필요한 물 및 에너지 등 비용과 환경부담을 상대적으로 크게 절감할 수 있는 전기이중층 캐패시터용 전극재의 제조방법을 제공하고자 한 것이다.Therefore, in order to improve the above, the present invention uses a commercially available activated carbon that is manufactured in large quantities at low cost by using starting materials that can be obtained in a relatively large amount, and then eluting impurities from alkaline and acid solutions. Method of manufacturing an electrode material for an electric double layer capacitor, which can significantly reduce the cost and environmental burden such as the activation aid input to the manufacturing process and the water and energy required for cleaning by drying and heat treatment in an inert atmosphere or a reducing ingredient atmosphere. It is intended to provide.
본 발명은 상용의 활성탄을 원료로 하여 (a)0.1mol/L ~ 포화농도의 알칼리용액으로 처리하여 불순물을 제거하는 단계; (b)상기 활성탄을 0.1mol/L ~ 포화농도의 산용액으로 처리하여 불순물을 제거하는 단계; (c)물로 세척 및 건조하는 단계; 및 (d)불활성분위기 또는 환원성분위기에서 300~1200℃로 5분 ~ 10시간 동안 열처리하는 단계; 를 포함하는 것이 특징이다.The present invention comprises the steps of removing impurities by using a commercial activated carbon as a raw material (a) 0.1mol / L ~ saturated alkali solution; (b) removing impurities by treating the activated carbon with an acid solution of 0.1 mol / L to a saturated concentration; (c) washing and drying with water; (D) heat treatment at 300 to 1200 ° C. for 5 minutes to 10 hours in an inert atmosphere or a reducing component atmosphere; It is characterized by including.
본 발명의 방법에 의하여 전극재를 제조할 경우 기존의 화학적 활성화 방법에 의하여 제조되는 전극재의 제조공정과 비교하여 원재료 중 가장 큰 비중을 차지하는 다량의 활성화조제의 사용이 불필요하여 이에 따른 세척수의 소요량 및 폐수의 발생량 등이 크게 저감할 수 있으므로 원가 및 환경에의 부담이 매우 적은 전극재의 제조가 가능하다. 이와 같이 제조된 전극재는 전기이중층 캐패시터의 전극으로 활용 시 화학적 활성화 방법에 의하여 제조된 전극재에 비하여 용량은 다소 저하되나 원가를 크게 절감할 수 있으므로 상대적으로 크게 높은 용량을 필요로 하지 않는 전기이중층 캐패시터의 전극재로서 활용이 가능하다.In the case of manufacturing the electrode material by the method of the present invention, compared to the manufacturing process of the electrode material manufactured by the conventional chemical activation method, it is unnecessary to use a large amount of activating aid that occupies the largest proportion of the raw materials, thus the required amount of washing water and Since the amount of waste water generated can be greatly reduced, it is possible to manufacture an electrode material having a very low cost and environmental burden. The electrode material manufactured as described above has a slightly lower capacity than the electrode material manufactured by the chemical activation method when used as an electrode of an electric double layer capacitor, but can significantly reduce costs, and thus does not require a relatively large capacity. Can be utilized as an electrode material.
본 발명은 상용의 활성탄을 원료로 하여 알칼리용액으로 처리하는 단계, 상기 활성탄을 산용액으로 처리하는 단계, 물로 세척 및 건조하는 단계, 불활성분위기 또는 환원성분위기에서 열처리하는 단계를 포함하는 전기이중층 캐패시터용 전 극재(탄소전극)의 제조방법으로 구성된다. The present invention is an electric double layer capacitor comprising the steps of treating the activated carbon as a raw material with an alkaline solution, treating the activated carbon with an acid solution, washing and drying with water, and heat treatment in an inert or reducing atmosphere. It consists of a method of manufacturing an electrode material (carbon electrode).
즉, 본 발명은 상용의 활성탄을 원료로 하여 (a)0.1mol/L ~ 포화농도의 알칼리용액으로 처리하여 불순물을 제거하는 단계; (b)상기 활성탄을 0.1mol/L ~ 포화농도의 산용액으로 처리하여 불순물을 제거하는 단계; (c)물로 세척 및 건조하는 단계; 및 (d)불활성분위기 또는 환원성분위기에서 300~1200℃로 5분 ~ 10시간 동안 열처리하는 단계; 를 포함하는 것이 특징이다.That is, the present invention comprises the steps of removing impurities by treating with a commercially available activated carbon as a raw material (a) 0.1 mol / L ~ saturated alkali solution; (b) removing impurities by treating the activated carbon with an acid solution of 0.1 mol / L to a saturated concentration; (c) washing and drying with water; (D) heat treatment at 300 to 1200 ° C. for 5 minutes to 10 hours in an inert atmosphere or a reducing component atmosphere; It is characterized by including.
이하 본 발명을 보다 상세하게 단계별로 설명한다. Hereinafter, the present invention will be described step by step in more detail.
본 발명의 (a) 단계에서는 상용의 활성탄을 원료로 하여 알칼리용액으로 처리하여 알칼리에 용해되는 회분성분을 제거하게 된다. 본 발명에서 사용되는 활성탄은 수질 및 대기오염물질 정화용의 흡착재로서 상용으로 널리 생산되는 활성탄을 사용할 수 있으며 적합한 활성탄의 출발물질로는 야자각, 석탄, 목질계 등 모든 활성탄을 사용할 수 있으며 활성탄의 비표면적은 가급적 높은 것을 전기이중층 캐패시터의 전극으로 사용할 경우 제품의 충방전 용량을 높게 할 수 있으므로 바람직하나 세공구조에 따라서는 비표면적이 낮고 적절한 세공구조를 가진 경우 전극부피당의 충방전용량이 높게 유지될 수 있으므로 이를 제한하지는 않는다. 또한 분말상, 입상, 섬유상 등의 형태에 따라서는 크게 충방전 용량이 좌우되지 않으므로 또한 이를 제한할 필요는 없다. 이들의 활성탄을 먼저 알칼리용액과 접촉시켜 회분을 제거하는 공정을 거치게 되며 적절한 알칼리의 종류로는 수산화나트륨(NaOH), 수산화칼륨(KOH) 등의 강알칼리성 화합물을 사용할 수 있으며 그 밖의 물에 용해 가능한 알칼리성 화합물을 모두 사용할 수 있다. 알칼리용액의 물에 대한 농도는 0.1mol/L ~ 포화농도까지 사용이 가능하며 0.1mol/L 미만의 농도에서는 회분의 용출이 장시간 반응시켜도 충분히 용출되지 않으므로 바람직하지 않다. 처리방법은 활성탄을 알칼리용액에 투입하고 회전식 교반기 또는 공기 투입기 등을 이용하여 교반하는 일반적인 반응기를 이용하면 되며 처리온도는 상온에서도 가능하나 온도가 높을수록 반응속도가 상대적으로 증가하므로 상온에서 용액의 비등점 이하의 어느 온도에서나 처리가 가능하다. 활성탄의 입도는 분말상이면 좀더 용이하게 반응이 일어나나 너무 미분일 경우에는 여과 등의 공정이 곤란해지는 점을 감안하여 적절히 할 수 있으며 이를 제한하지는 않는다. 원료 활성탄 중에 알칼리용액에 용해 가능한 회분성분이 존재하지 않거나 캐패시터 전극재로서 활용 시에 불순물로서 영향을 주지 않을 정도로 미량인 경우에는 알칼리용액으로 처리하는 본 공정은 생략할 수도 있다.In step (a) of the present invention, the ash component dissolved in the alkali is removed by treating the activated carbon with an alkaline solution as a raw material. Activated carbon used in the present invention can be used commercially widely used as an adsorbent for water and air pollutant purification, and as a starting material of suitable activated carbon, any activated carbon such as coconut shell, coal, wood-based, etc. can be used. If the surface area is as high as possible, the charge and discharge capacity of the product can be increased when using the electrode of the electric double layer capacitor. However, the specific surface area is low depending on the pore structure, and the charge and discharge capacity per electrode volume can be maintained high. It does not limit this because it can. In addition, since the charge and discharge capacity does not largely depend on the form of powder, granule, fiber, etc., it is not necessary to limit this. These activated carbons are first contacted with an alkali solution to remove ash.As a suitable alkali type, strong alkaline compounds such as sodium hydroxide (NaOH) and potassium hydroxide (KOH) can be used and can be dissolved in other water. All alkaline compounds can be used. The concentration of the alkaline solution in water can be used at a concentration of 0.1 mol / L to saturation, and it is not preferable at the concentration of less than 0.1 mol / L because the elution of ash is not sufficiently eluted even if it reacts for a long time. The treatment method is to use a general reactor in which activated carbon is added to the alkaline solution and stirred using a rotary stirrer or an air injector, and the treatment temperature can be at room temperature, but the reaction rate is increased with higher temperature, so the boiling point of the solution at room temperature is increased. The treatment can be performed at any of the following temperatures. If the particle size of the activated carbon is in the form of powder, the reaction occurs more easily. However, if the powder is too fine, the particle size may be appropriate in view of difficulty in filtration and the like, but is not limited thereto. If the ash component which is soluble in the alkaline solution does not exist in the raw activated carbon, or is so small that it does not affect as an impurity when used as a capacitor electrode material, this step of treating with an alkaline solution may be omitted.
다음 공정으로서 (b) 단계에서는 상기 알칼리용액으로 처리한 활성탄을 다시 산용액으로 처리하는 단계를 거치게 된다. 야자각이나 석탄계 활성탄의 경우 포함되어 있는 회분성분 중 일부의 화합물은 알칼리에 용출되어 제거되나 용출되지 않은 많은 부분이 잔류하게 되므로 이를 산용액으로 처리하여 제거하고자 하는 공정이다. 적절한 산의 종류로는 질산(HNO3), 염산(HCl), 불산(HF), 황산(H2SO4), 왕수 등의 강산성 화합물을 모두 사용할 수 있으며 그 밖의 산을 모두 사용할 수 있다. 산용액의 물에 대한 농도는 0.1mol/L ~ 포화농도까지 사용이 가능하며 0.1mol/L 미만의 농도에서는 회분의 용출이 장시간 반응시켜도 충분히 용출되지 않으므로 바람직하지 않다. 처리방법은 알칼리용액 처리공정과 동일한 반응기를 이용하면 되며 처리온도도 알칼리용액 처리공정과 동일한 기준에 의하여 상온에서 용액의 비등점 이하의 온도에서 처리하면 된다. 원료 활성탄 중에 알칼리용액에 의한 처리 만으로서 회분성분이 불순물로서 영향을 주지 않을 정도로 미량 잔류하게 되는 경우 또는 산용액에 용해 가능한 회분성분이 존재하지 않는 경우에는 산용액으로 처리하는 본 공정은 생략할 수도 있으며 산용액에 의한 처리하는 본 공정을 알칼리용액에 의한 처리하는 앞의 공정보다 먼저 실시하는 것도 무방하다.In the next step (b), the activated carbon treated with the alkaline solution is treated with an acid solution again. In the case of coconut shell or coal-based activated carbon, some of the compounds contained in the ash component are eluted and removed by alkali, but many of the components are not eluted. Suitable acid types include all strong acid compounds such as nitric acid (HNO 3 ), hydrochloric acid (HCl), hydrofluoric acid (HF), sulfuric acid (H 2 SO 4 ), aqua regia, and all other acids. The concentration of the acid solution in water can be used at a concentration of 0.1 mol / L to saturation, and the concentration of the acid solution is less than 0.1 mol / L. The treatment method may be the same reactor as the alkaline solution treatment step, and the treatment temperature may be treated at a temperature below the boiling point of the solution at room temperature according to the same criteria as the alkaline solution treatment step. If the ash component remains in a trace amount only by treatment with alkaline solution in the raw activated carbon, or if there is no ash component that can be dissolved in the acid solution, this step of treating with acid solution may be omitted. In addition, this step of treating with an acid solution may be performed before the previous step of treating with an alkaline solution.
다음 공정으로서 (c) 단계에서는 알칼리용액과 산용액으로 처리된 활성탄은 물로 세척하고 건조하여 용출된 이물질을 제거하게 된다. 세척공정은 통상의 활성탄의 세척방법에 의하여 물로서 세척하여 제거하면 되며 건조공정은 통상의 활성탄의 건조방법에 의하여 적정온도에서 적정시간 동안 건조하면 된다.In the next step (c), activated carbon treated with an alkaline solution and an acid solution is washed with water and dried to remove the eluted foreign matter. The washing process may be removed by washing with water by a conventional method of washing activated carbon, and the drying process may be dried for a proper time at an appropriate temperature by a drying method of ordinary activated carbon.
다음 공정으로서 (d) 단계에서는 이와 같이 알칼리와 산에 의하여 회분이 제거된 활성탄을 불활성분위기 또는 환원성분위기에서, 300~1200℃에서 5분 ~ 10시간 동안 열처리하는 단계를 거치게 된다. 이 단계는 산처리에 의하여 표면에 형성된 화학 관능기들이 전기이중층 캐패시터의 전극재로 작용 시에 부반응을 일으켜 캐패시터를 팽창시키거나 또한 충방전의 반복 시에 전해액과의 화학반응에 의하여 용량저하를 일으키는 것을 방지하기 위한 것이다. 열처리온도는 300~1200℃에서 실시하는 것이 적절하며 300℃ 미만으로 열처리하는 경우 10시간 이상 장기간 열처리하여도 표면의 관능기들의 분해가 이루어지지 않으므로 바람직하지 않으며 1200℃ 이상으로 열처리하는 경우에는 5분 정도의 단시간 동안 열처리하여도 활성탄의 구조가 결정화가 일어나서 세공의 합체 등에 의하여 비표면적이 감소하여 캐패시터 제작 시에 충방전 용량이 감소하게 되므로 바람직하지 않다. 열처리분위기는 활성탄의 표면에 산소를 함유하는 관능기들이 많이 분포하므로 수소 또는 암모니아등과 같은 환원성분위기에서 실시할 경우 보다 용이하게 산소함유 관능기를 환원반응에 의하여 제거할 수 있으며 질소, 헬륨, 알곤, 이산화탄소 등과 같은 불활성분위기에서 열처리하는 것으로도 표면관능기의 열분해에 의한 제거가 가능하며 환원성 기체와 불활성기체를 적절한 비율로 혼합한 분위기에서의 열처리도 바람직한 방법의 하나이며 산소가 포함되어 있는 산화성 기체 이외의 분위기에서는 모두 열처리가 가능하다.In the next step (d), the activated carbon from which ash is removed by alkali and acid is subjected to a heat treatment for 5 minutes to 10 hours at 300 to 1200 ° C. in an inert or reducing atmosphere. In this step, chemical functional groups formed on the surface by acid treatment cause side reactions when they act as electrode materials of the electric double layer capacitors to expand the capacitors, or to decrease capacity due to chemical reactions with the electrolyte upon repeated charge and discharge. It is to prevent. The heat treatment temperature is appropriately performed at 300 ~ 1200 ℃, and the heat treatment below 300 ℃ is not preferable because the functional groups on the surface are not decomposed even after long term heat treatment for over 10 hours. Even after heat treatment for a short time, the structure of activated carbon is crystallized and the specific surface area is reduced due to the incorporation of pores, so that the charge / discharge capacity is decreased during capacitor production. In the heat treatment atmosphere, since oxygen-containing functional groups are distributed on the surface of activated carbon, oxygen-containing functional groups can be more easily removed by reduction reaction when carried out in a reducing component such as hydrogen or ammonia, and nitrogen, helium, argon and carbon dioxide. It is possible to remove the surface functional group by thermal decomposition by heat treatment in an inert atmosphere such as, etc., and heat treatment in an atmosphere in which a reducing gas and an inert gas are mixed at an appropriate ratio is one of the preferred methods, and it is an atmosphere other than oxidizing gas containing oxygen. In all, heat treatment is possible.
이와 같은 전기이중층 캐패시터용 전극재의 제조방법은 화학적 활성화 방법에 의하여 제조하는 방법에 비하여 제조공정에 투입되는 활성화조제가 불필요하며 세척에 필요한 물 및 에너지가 크게 절감되어 비용과 환경부담을 상대적으로 크게 절감할 수 있다.Such a method of manufacturing an electrode material for an electric double layer capacitor has no need for an activation aid to be put into the manufacturing process compared to a method of manufacturing by chemical activation, and greatly reduces water and energy required for cleaning, thereby significantly reducing cost and environmental burden. can do.
이하, 본 발명의 이해를 돕기 위하여 바람직한 실시예를 제시한다. 그러나 하기의 실시예는 본 발명을 보다 쉽게 이해하기 위하여 제공되는 것일 뿐 본 발명이 하기의 실시예에 한정되는 것은 아니다. Hereinafter, preferred examples are provided to aid in understanding the present invention. However, the following examples are provided only to more easily understand the present invention, and the present invention is not limited to the following examples.
[실시예 1] Example 1
야자각을 원료로 하여 제조된 비표면적 1180m2/g의 활성탄을 5mol/L농도의 수산화나트륨 수용액 중에서 80℃로 가열하면서 2시간 처리한 후 이를 다시 5mol/L 농도의 질산용액에서 80℃에서 2시간 처리하여 불순물을 제거하였다. 이를 pH가 6.8에 이르기까지 물로 세척하고150℃에서 상압에서 건조하였다. 이때 활성탄 1g당 약 50ml의 세척수가 소요되었다. 이 활성탄을 계속하여 부피기준 수소 5% 및 잔여부분은 질소로 이루어진 혼합기체 분위기에서 600℃로 1시간 동안 열처리하여 전극재를 제조하였다. Activated carbon with a specific surface area of 1180 m 2 / g prepared using coconut shell was treated for 2 hours while heating to 80 ° C. in a 5 mol / L sodium hydroxide aqueous solution, and then again treated at 80 ° C. in a 5 mol / L nitric acid solution. Time treatment removes impurities. It was washed with water until the pH reached 6.8 and dried at 150 ° C. at atmospheric pressure. At this time, about 50 ml of washing water was used per 1 g of activated carbon. The activated carbon was subsequently heat treated at 600 ° C. for 1 hour in a mixed gas atmosphere composed of 5% by volume hydrogen and the remaining part to prepare an electrode material.
이를 20㎛ 이하로 분쇄하여 전극물질로 하여 Carbon black을 도전재로 사용하고 PTFE(Polytetrafluoroethylene)을 결합재로 사용하고 유기전해액을 사용하여 코인셀형 전기이중층 캐패시터를 제작하였다. 그 결과 축전용량은 85F/g을 나타내었다.It was pulverized to 20㎛ or less, using carbon black as the conductive material, PTFE (Polytetrafluoroethylene) as a binder and an organic electrolyte solution to produce a coin cell type electric double layer capacitor. As a result, the storage capacity was 85F / g.
[실시예 2] Example 2
실시예1에서의 야자각 활성탄을 포화농도의 수산화나트륨 수용액 중에서 80℃로 가열하면서 2시간 처리한 후 이를 다시 왕수원액을 80℃로 2시간 처리하여 불순물을 제거하였다. 이를 pH가 6.8에 이르기까지 물로 세척하고 150℃에서 상압에서 건조하였다. 이때 활성탄 1g당 약 70ml의 세척수가 소요되었다. 이 활성탄을 계속하여 부피기준 수소 5% 및 잔여부분은 질소로 이루어진 혼합기체 분위기에서 600℃로 1시간 동안 열처리하여 전극재를 제조하였다. After treating the coconut shell activated carbon in Example 1 with a saturated sodium hydroxide aqueous solution at 80 ° C. for 2 hours, the aqua regia solution was treated at 80 ° C. for 2 hours to remove impurities. It was washed with water until the pH reached 6.8 and dried at 150 ° C. at atmospheric pressure. At this time, about 70ml of washing water was used per 1g of activated carbon. The activated carbon was subsequently heat treated at 600 ° C. for 1 hour in a mixed gas atmosphere composed of 5% by volume hydrogen and the remaining part to prepare an electrode material.
이를 실시예1과 동일한 조건으로 코인셀형 전기이중층 캐패시터를 제작하였다. 그 결과 축전용량은 102F/g을 나타내었다.A coin cell type electric double layer capacitor was manufactured under the same conditions as in Example 1. As a result, the storage capacity was 102F / g.
[실시예 3] Example 3
석탄을 원료로 하여 제조된 비표면적 985m2/g의 활성탄을 실시예2와 같은 조건으로 포화농도의 수산화나트륨 수용액 중에서 80℃로 가열하면서 2시간 처리한 후 이를 다시 왕수원액을 80℃로 2시간 처리하여 불순물을 제거하였다. 이를 pH가 6.8에 이르기까지 물로 세척하고 150℃에서 상압에서 건조하였다. 이때 활성탄 1g당 약 70ml의 세척수가 소요되었다. 이 활성탄을 계속하여 부피기준 수소 5% 및 잔여부분은 질소로 이루어진 혼합기체 분위기에서 600℃로 1시간 동안 열처리하여 전극재를 제조하였다. Activated carbon with a specific surface area of 985 m 2 / g prepared from coal was treated for 2 hours while heating to 80 ° C. in a saturated aqueous sodium hydroxide solution under the same conditions as in Example 2, and then the aqua rejuvenation solution was returned to 80 ° C. for 2 hours. Treatment removes impurities. It was washed with water until the pH reached 6.8 and dried at 150 ° C. at atmospheric pressure. At this time, about 70ml of washing water was used per 1g of activated carbon. The activated carbon was subsequently heat treated at 600 ° C. for 1 hour in a mixed gas atmosphere composed of 5% by volume hydrogen and the remaining part to prepare an electrode material.
이를 실시예1과 동일한 조건으로 코인셀형 전기이중층 캐패시터를 제작하였다. 그 결과 축전용량은 77F/g을 나타내었다.A coin cell type electric double layer capacitor was manufactured under the same conditions as in Example 1. As a result, the storage capacity was 77F / g.
[비교예 1] Comparative Example 1
석유계 코크스를 원료로 하여 코크스 1g당 활성화조제로서 KOH 4g을 혼합하여 700℃에서 1시간 동안 열처리하여 얻어진 고형의 혼합물을 다량의 물에 넣어 80℃로 가열하면서 활성화 조제를 용출시키고 물로 교반하면서 세척후의 세척수의 pH가 7.5미만이 되도록 20회 세척하였다. 이를 150℃에서 진공건조하여 전극재를 제 조하였다. 제조된 전극재 1g당 약 3000ml의 세척수가 소요되었다.Using petroleum coke as a raw material, 4 g of KOH was mixed as an activating aid per 1 g of coke, and the solid mixture obtained by heat treatment at 700 ° C. for 1 hour was added to a large amount of water, heated to 80 ° C. to elute the activating aid and washed with water. The wash water was washed 20 times so that the pH of the wash water was less than 7.5. This was vacuum dried at 150 ° C. to prepare an electrode material. About 3000 ml of washing water was used per 1 g of the prepared electrode material.
이를 20㎛ 이하로 분쇄하여 전극물질로 하여 Carbon black을 도전재로 사용하고 PTFE(Polytetrafluoroethylene)을 결합재로 사용하고 유기전해액을 사용하여 코인셀형 전기이중층형 캐패시터를 제작하였다. 그 결과 축전용량은 125F/g을 나타내었다.It was pulverized to 20㎛ or less, using carbon black as the conductive material, PTFE (Polytetrafluoroethylene) as a binder and an organic electrolyte solution to produce a coin cell type electric double layer capacitor. As a result, the storage capacity was 125F / g.
[비교예 2]Comparative Example 2
실시예 1에서의 야자각을 원료로 하여 제조된 상용의 활성탄을 20㎛ 이하로 분쇄하고 이를 150℃에서 진공건조한 것을 그대로 전극물질로 하여 Carbon black을 도전재로 사용하고 PTFE(Polytetrafluoroethylene)을 결합재로 사용하고 유기전해액을 사용하여 코인셀형 전기이중층형 캐패시터를 제작하였다. 그 결과 축전용량은 55F/g을 나타내었으며 평가를 위하여 제작된 캐패시터는 충방전의 반복에 따라 전해액과의 부반응에 의한 크게 부풀어오르는 현상을 나타내었다.The activated activated carbon prepared in Example 1 was ground to 20 µm or less and vacuum dried at 150 ° C. as an electrode material. Carbon black was used as a conductive material, and PTFE (Polytetrafluoroethylene) was used as a binder. And a coin cell type electric double layer capacitor was prepared using the organic electrolyte solution. As a result, the storage capacity was 55F / g, and the capacitor manufactured for evaluation showed a swelling phenomenon due to side reaction with the electrolyte with repeated charge and discharge.
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| KR101366522B1 (en) * | 2012-08-07 | 2014-02-24 | 재영솔루텍 주식회사 | Method for cleaning metal-resin combination and method for fabricating electrode terminal assembly of battery using the same |
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| EP1675141B1 (en) * | 2003-10-17 | 2018-01-03 | Power Carbon Technology Co., Ltd. | Method for producing activated carbon for electrode |
| KR101035620B1 (en) * | 2004-09-24 | 2011-05-19 | 삼성에스디아이 주식회사 | Electrode for fuel cell, fuel cell comprising the same, and method for preparing the electrode |
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| US9101941B2 (en) | 2011-04-06 | 2015-08-11 | Korea Institute Of Construction Technology | Activated carbon for simultaneous removal of dust and gaseous air pollutants and method of preparing activated carbon electrode plate using the same |
| KR101366522B1 (en) * | 2012-08-07 | 2014-02-24 | 재영솔루텍 주식회사 | Method for cleaning metal-resin combination and method for fabricating electrode terminal assembly of battery using the same |
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