JP3038676B2 - Electric double layer capacitor - Google Patents
Electric double layer capacitorInfo
- Publication number
- JP3038676B2 JP3038676B2 JP63068247A JP6824788A JP3038676B2 JP 3038676 B2 JP3038676 B2 JP 3038676B2 JP 63068247 A JP63068247 A JP 63068247A JP 6824788 A JP6824788 A JP 6824788A JP 3038676 B2 JP3038676 B2 JP 3038676B2
- Authority
- JP
- Japan
- Prior art keywords
- less
- electric double
- double layer
- ppm
- activated carbon
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000003990 capacitor Substances 0.000 title claims description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 50
- 239000008151 electrolyte solution Substances 0.000 claims description 10
- 239000011148 porous material Substances 0.000 claims description 9
- 239000003792 electrolyte Substances 0.000 claims description 8
- 239000012535 impurity Substances 0.000 claims description 8
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 6
- 244000060011 Cocos nucifera Species 0.000 claims description 6
- 239000003125 aqueous solvent Substances 0.000 claims description 3
- 238000000034 method Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- -1 polytetrafluoroethylene Polymers 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229940021013 electrolyte solution Drugs 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 239000004745 nonwoven fabric Substances 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 238000010000 carbonizing Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 235000002639 sodium chloride Nutrition 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 235000011162 ammonium carbonates Nutrition 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 235000011148 calcium chloride Nutrition 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000002788 crimping Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000010903 husk Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- RHFUXPCCELGMFC-UHFFFAOYSA-N n-(6-cyano-3-hydroxy-2,2-dimethyl-3,4-dihydrochromen-4-yl)-n-phenylmethoxyacetamide Chemical compound OC1C(C)(C)OC2=CC=C(C#N)C=C2C1N(C(=O)C)OCC1=CC=CC=C1 RHFUXPCCELGMFC-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 238000007750 plasma spraying Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 150000005621 tetraalkylammonium salts Chemical class 0.000 description 1
- 125000005497 tetraalkylphosphonium group Chemical group 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
- H01G11/58—Liquid electrolytes
- H01G11/62—Liquid electrolytes characterised by the solute, e.g. salts, anions or cations therein
-
- 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
-
- 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)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Materials Engineering (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明は電気二重層コンデンサに関するものである。The present invention relates to an electric double layer capacitor.
［従来の技術］ 電気二重層コンデンサに従来用いられてきた分極性電
極としては、活性炭、活性炭繊維等種々の素材があげら
れる。[Prior Art] Various materials such as activated carbon and activated carbon fiber can be used as polarizable electrodes conventionally used in electric double layer capacitors.
活性炭を用いた例としては、活性炭の粉末を電解液と
混合してペースト化して用いる電極が提案されている
（特公昭55-41015号公報）。As an example using activated carbon, there has been proposed an electrode in which activated carbon powder is mixed with an electrolytic solution to form a paste (Japanese Patent Publication No. 55-41015).
［発明の解決しようとする課題］ しかしながら、このようなペースト電極に使用される
活性炭の比表面積は、1500m2/g以下であり、この電極を
用いたコンデンサは単位体積当りの容量が必ずしも十分
ではなかった。また、活性炭の製造工程は、通常、原料
の炭化・賦活の工程と粉砕工程とよりなり、原料の炭化
・賦活には薬品賦活あるいはガス賦活の方法が適用され
ることが多い。したがって、高比表面積を有する活性炭
を得ようとする場合、高温度で長時間の賦活条件が要求
されるため、反応工程中に反応容器からの重金属分が活
性炭粉末中に混入して、得られる活性炭の純度が低下す
るという問題点があった。さらに粉砕工程中に金属など
の不純物が活性炭に混入することが少なくなかった。こ
のため、従来の電気二重層コンデンサにおいては、分極
性電極を形成する活性炭が多くの不純物を含有してお
り、特に高温度負荷条件下において、電解液中に金属そ
の他の不純物が溶出して電気化学的反応を引起こすこと
によってコンデンサの長期信頼性が損なわれるという問
題点があった。[Problems to be Solved by the Invention] However, the specific surface area of activated carbon used for such a paste electrode is 1500 m 2 / g or less, and a capacitor using this electrode does not always have a sufficient capacity per unit volume. Did not. In addition, the production process of activated carbon usually includes a process of carbonizing and activating a raw material and a pulverizing process, and a method of chemical activation or gas activation is often applied to carbonizing and activating the raw material. Therefore, when trying to obtain an activated carbon having a high specific surface area, the activation condition for a long time at a high temperature is required, so that the heavy metal component from the reaction vessel is mixed into the activated carbon powder during the reaction step and is obtained. There was a problem that the purity of activated carbon was reduced. Furthermore, during the pulverizing step, impurities such as metals were often mixed into the activated carbon. For this reason, in the conventional electric double-layer capacitor, the activated carbon forming the polarizable electrode contains many impurities. There is a problem that the long-term reliability of the capacitor is impaired by causing a chemical reaction.
［課題を解決するための手段］ 本発明者はこれら諸問題を解決することを目的として
種々研究検討した結果、この様な活性炭に対し、他の成
分を添加して悪影響を解決するよりも、前記不純物の許
容量を特定化することにより、かえって安定した活性を
長期にわたり持続し得る電極を得ることが可能になるこ
とを知見し、本発明の目的を達成し得ることを見出し
た。[Means for Solving the Problems] As a result of various studies and studies for the purpose of solving these problems, the present inventor has found that rather than adding other components to such activated carbon to solve the adverse effects, It has been found that by specifying the allowable amount of the impurity, it is possible to obtain an electrode capable of maintaining stable activity over a long period of time, and has found that the object of the present invention can be achieved.
かくして本発明は、分極性電極と電解液の界面で形成
される電気二重層を利用する電気二重層コンデンサにお
いて、不純物であるFeが100ppm以下、Crが5ppm以下、Ni
が5ppm以下、Naが150ppm以下、Ｋが100ppm以下、Clが10
0ppm以下で、灰分が0.5％以下のヤシガラ活性炭よりな
る分極性電極を用いることを特徴とする電気二重層コン
デンサを提供するにある。Thus, the present invention provides an electric double layer capacitor utilizing an electric double layer formed at the interface between the polarizable electrode and the electrolyte, wherein the impurities Fe are 100 ppm or less, Cr is 5 ppm or less, Ni
Is 5 ppm or less, Na is 150 ppm or less, K is 100 ppm or less, Cl is 10 ppm or less.
It is an object of the present invention to provide an electric double layer capacitor using a polarizable electrode made of coconut shell activated carbon having an ash content of 0 ppm or less and 0.5% or less.
分極性電極に用いる活性炭の原料としてオガクズ等木
質系、フェノール樹脂、ピッチ等樹脂系があるが、前者
は1500m2/g以上の高比表面積を得ることは難しく、また
不純物含有量も大きく、また後者は比表面積を上げるこ
とは容易であるが、コストが非常に割高となる欠点があ
り、本発明ではこれらの諸欠点を有さない原料としてヤ
シガラを用いる。Sawdust and the like woody as a raw material of the activated carbon used for the polarized electrode, phenolic resin, there is a pitch or the like resin, the former it is difficult to obtain the above high specific surface area 1500 m 2 / g, and impurity content is large, also The latter is easy to increase the specific surface area, but has a disadvantage that the cost is very high. In the present invention, coconut husk is used as a raw material that does not have these disadvantages.
本発明で使用するヤシガラを原料とする活性炭が含有
する不純物量としてはFeが100ppm以下、Crが5ppm以下、
Niが5ppm以下、Naが150ppm以下、Ｋが100ppm以下、Clが
100ppm以下であり灰分が0.5％以下好ましくは0.4％以下
である。活性炭の不純物含有量が前記範囲を逸脱する
と、長期信頼性に著しい悪影響を及ぼすので不適当であ
る。As the amount of impurities contained in the activated carbon made from coconut shell used in the present invention, Fe is 100 ppm or less, Cr is 5 ppm or less,
Ni is 5ppm or less, Na is 150ppm or less, K is 100ppm or less, Cl is
It is 100 ppm or less and the ash content is 0.5% or less, preferably 0.4% or less. If the impurity content of the activated carbon is out of the above range, the long-term reliability is significantly adversely affected, which is not appropriate.
また活性炭の物性としては比表面積が1500〜1900m2/g
好ましくは1650〜1850m2/gが適当である。Activated carbon has a specific surface area of 1500 to 1900 m 2 / g
Preferably, 1650 to 1850 m 2 / g is suitable.
これ以上の比表面積を有する活性炭を得ようとする
と、収率が低下するので実際的ではない。又、平均細孔
径としては13〜20Å好ましくは14〜19Å、全細孔容積と
しては0.6〜0.9ml/g好ましくは0.65〜0.8ml/gであり、
細孔径20Å以上の細孔の容積が全細孔容積に対して30〜
50％好ましくは35〜45％のものが好適である。It is not practical to obtain activated carbon having a specific surface area greater than this, since the yield is reduced. Also, the average pore diameter is 13 to 20 mm, preferably 14 to 19 mm, and the total pore volume is 0.6 to 0.9 ml / g, preferably 0.65 to 0.8 ml / g,
The volume of pores with a pore diameter of 20 mm or more is 30 to
Those with 50%, preferably 35-45% are suitable.
本発明で用いる電極としては、この活性炭粉末を電解
液と混合してペースト化したものを電極として用いるこ
とも可能である。しかしながら、単位体積当りの容積と
機械的強度のさらに良好な電極としては、ポリテトラフ
ルオロエチレン（以下、PTFEと略称する）などの耐化学
薬品性の優れた結着剤を用いて活性炭粉末をシート化し
てなる電極があげられる。このようなシート状電極とし
ては、まず活性炭微粉末に対して好ましくは１〜50重量
％、さらに好ましくは５〜30重量％の好ましくはPTFEを
混合し、得られた粘稠な混合物を圧縮、押出し、もしく
は圧延、またはこれらの手段を組合せることによってシ
ート状に成形したものが好適に使用できる。As the electrode used in the present invention, a paste obtained by mixing this activated carbon powder with an electrolytic solution can be used. However, as an electrode having better volume per unit volume and better mechanical strength, a sheet of activated carbon powder using a chemical-resistant binder such as polytetrafluoroethylene (hereinafter abbreviated as PTFE) is used. Electrodes. As such a sheet-shaped electrode, first, preferably 1 to 50% by weight, more preferably 5 to 30% by weight, of PTFE is preferably mixed with the activated carbon fine powder, and the obtained viscous mixture is compressed. A sheet formed by extrusion, rolling, or a combination of these means can be suitably used.
このシート状成形物は、さらに必要に応じて一軸方
向、または二軸方向に延伸処理される。この延伸処理
は、20〜380℃好ましくは20〜200℃において、好ましく
は原長の1.1〜5.0倍、特に好ましくは1.2〜2.0倍になる
ように公知の方法（たとえば、特開昭59-166541号公
報）により行なわれる。このようにして得られた延伸処
理物は、そのまま使用することもできるが、必要に応じ
て、さらにロール、プレスなどにより圧延または圧縮処
理した後、焼成または半焼成処理して使用する。This sheet-like molded product is further stretched in a uniaxial direction or a biaxial direction as necessary. This stretching treatment is carried out at a temperature of 20 to 380 ° C., preferably 20 to 200 ° C., preferably 1.1 to 5.0 times, more preferably 1.2 to 2.0 times the original length (for example, JP-A-59-166541). Gazette). The thus obtained stretched product can be used as it is. However, if necessary, it is rolled or compressed by a roll, a press or the like, and then fired or semi-fired.
本発明で活性炭よりなる分極性電極と組合せて使用す
る電解液は特に限定されるものではなく、電気二重層コ
ンデンサ用として使用可能なもの、すなわち、非水溶媒
系または水溶液系電解液が適宜使用される。The electrolytic solution used in combination with the polarizable electrode made of activated carbon in the present invention is not particularly limited, and those usable for electric double layer capacitors, that is, non-aqueous solvent-based or aqueous electrolyte solutions are appropriately used. Is done.
本発明で活性炭よりなる分極性電極と組合せて使用さ
れる非水溶媒系電解液としては、たとえば過塩素酸、６
フッ化リン酸、４フッ化ホウ酸、トリフルオロメタンス
ルホン酸などのテトラアルキルアンモニウム塩、テトラ
アルキルホスホニウム塩、またはアミン塩などの溶質
を、プロピレンカーボネート、γ−ブチロラクトン、ア
セトニトリル、ジメチルホルムアミド、1,2−ジメトキ
シエタン、スルホラン、ニトロメタンなどの極性有機溶
媒に0.3〜1.5M/l程度溶解させたものがあげられる。The non-aqueous solvent-based electrolyte used in combination with the polarizable electrode made of activated carbon in the present invention includes, for example, perchloric acid, 6
Solutes such as tetraalkylammonium salts such as fluorophosphoric acid, tetrafluoroboric acid and trifluoromethanesulfonic acid, tetraalkylphosphonium salts or amine salts are converted to propylene carbonate, γ-butyrolactone, acetonitrile, dimethylformamide, 1,2 And-about 0.3 to 1.5 M / l dissolved in a polar organic solvent such as dimethoxyethane, sulfolane, and nitromethane.
活性炭よりなる分極性電極と組合せて用いる水溶液系
電解液としては、高い電気伝導性を有する無機酸、無機
塩基、または無機塩を溶質とするものが好適である。こ
のような電解液の溶質（電解質）としては、たとえば硫
酸、４フッ化ホウ酸、硝酸などの酸、水酸化カリウム、
水酸化ナトリウム、水酸化カルシウム、水酸化アンモニ
ウムなどの塩基、塩化カリウム、塩化ナトリウム、塩化
カルシウム、塩化アンモニウムなどの塩化物、炭酸カリ
ウム、炭酸ナトリウム、炭酸カルシウム、炭酸アンモニ
ウムなどの炭酸塩等が好適に使用される。これらの電解
質の中で、硫酸、４フッ化ホウ酸、水酸化カリウムおよ
び水酸化ナトリウムは、高い伝導度が得られる点で特に
好ましい。As the aqueous electrolyte solution to be used in combination with the polarizable electrode made of activated carbon, a solution containing an inorganic acid, an inorganic base, or an inorganic salt having high electric conductivity as a solute is preferable. Examples of the solute (electrolyte) of such an electrolytic solution include acids such as sulfuric acid, tetrafluoroboric acid and nitric acid, potassium hydroxide,
Bases such as sodium hydroxide, calcium hydroxide and ammonium hydroxide, chlorides such as potassium chloride, sodium chloride, calcium chloride and ammonium chloride, and carbonates such as potassium carbonate, sodium carbonate, calcium carbonate and ammonium carbonate are preferred. used. Among these electrolytes, sulfuric acid, tetrafluoroboric acid, potassium hydroxide and sodium hydroxide are particularly preferred in that high conductivity is obtained.
水溶液系電解液の濃度は、10〜90重量％の範囲で適宜
選定することができ、一般に90重量％以上の濃度になる
と寒冷時に溶質が析出するなどの問題が発生し、また10
重量％以下の濃度では、電導度が低下してコンデンサの
内部抵抗を増大させるので好ましくない。The concentration of the aqueous electrolyte solution can be appropriately selected within the range of 10 to 90% by weight. In general, when the concentration is 90% by weight or more, problems such as precipitation of solutes in cold conditions occur.
If the concentration is less than% by weight, the electric conductivity decreases and the internal resistance of the capacitor increases, which is not preferable.
前述のシート状物をコンデンサの形状に合せて加工・
成形した電極間に多孔質のセパレータを挟み、前記のよ
うな電解液を含浸または満たしてケース中に密閉するこ
とによって本発明による電気二重層コンデンサが得られ
る。Process the above-mentioned sheet according to the shape of the capacitor.
An electric double-layer capacitor according to the present invention can be obtained by sandwiching a porous separator between the formed electrodes, impregnating or filling the above-described electrolytic solution, and sealing the inside of the case.
多孔質セパレータとしては、たとえば、ポリプロピレ
ン繊維不織布、ガラス繊維混抄不織布などが好適に使用
できる。また、セパレータの厚みは50〜200μｍが適当
であり、100〜150μｍとするのが特に好適である。As the porous separator, for example, a polypropylene fiber nonwoven fabric, a glass fiber mixed nonwoven fabric and the like can be suitably used. The thickness of the separator is suitably from 50 to 200 μm, and particularly preferably from 100 to 150 μm.
また本発明で用いる分極性電極からの集電方法も特に
限定されるものではなく、従来から周知、公知の方法が
使用可能である。例えば金属ケースに金属網を溶接しそ
の上に電極を圧着したり、電極上にプラズマ溶射、メッ
キ等によって金属集電を形成したり、或は導電性接着剤
によって接着する方法等が好ましく使用可能である。特
に炭素質を含む導電性接着剤を用いる方法が好ましい。The method for collecting electricity from the polarizable electrode used in the present invention is not particularly limited, and a conventionally well-known method can be used. For example, a method of welding a metal net to a metal case and crimping the electrode thereon, forming a metal current collector on the electrode by plasma spraying, plating, or the like, or bonding with a conductive adhesive can be preferably used. It is. In particular, a method using a conductive adhesive containing carbonaceous material is preferable.
本発明に用いられる導電性接着剤としては、バインダ
ーをほとんど含まない高純度黒鉛系のものが好ましい
が、フェノールなどの樹脂系バインダもしくは水ガラス
などの無機質バインダを含む黒鉛あるいはカーボンブラ
ック系の導電性接着剤なども用いることができる。As the conductive adhesive used in the present invention, a high-purity graphite-based material containing almost no binder is preferable, but a graphite or carbon black-based conductive material containing a resin binder such as phenol or an inorganic binder such as water glass is preferred. An adhesive or the like can also be used.
［実施例］ 以下、本発明の実施例および比較例を図面を参照して
具体的に説明する。EXAMPLES Examples and comparative examples of the present invention will be specifically described below with reference to the drawings.
第１表に示した各種のヤシガラ活性炭70重量％、カー
ボンブラック20重量％およびPTFE（粒子径0.3μｍ）10
重量％よりなる粉末混合物100重量部に対して水200重量
部を添加し、Ｖ形ブレンダー中で混和した。得られたペ
ースト状混和物をロール成形機を用いて圧延し、厚さ1.
1mmのシートとした。このシートを300℃に予熱した状態
で一軸方向に1.1倍の倍率で延伸処理して厚さ0.6mmのシ
ート状電極材料を得た。70% by weight of various types of coconut shell activated carbon shown in Table 1, 20% by weight of carbon black and PTFE (particle diameter 0.3 μm) 10
200 parts by weight of water was added to 100 parts by weight of the powder mixture consisting of 100% by weight and mixed in a V-type blender. The obtained paste-like admixture was rolled using a roll forming machine to a thickness of 1.
A 1 mm sheet was used. The sheet was preheated to 300 ° C. and stretched in a uniaxial direction at a magnification of 1.1 times to obtain a sheet-like electrode material having a thickness of 0.6 mm.
このシート状電極材料を使用して第１図に示すような
コイン型電気二重層コンデンサのユニットセル（直径20
mm、厚さ2.0mm）を下記の手順で作製した。A unit cell (diameter of 20) of a coin-type electric double layer capacitor as shown in FIG.
mm, thickness 2.0 mm) was produced by the following procedure.
前記シート状電極材料を円板状に打ち抜いて分極性電
極１および２（直径15mm、厚さ0.6mm）とし、この分極
性電極１、２をポリプロピレン繊維不織布よりなるセパ
レータ３を介してステンレス鋼製のキャップ４およびス
テンレス鋼製の缶５からなる外装容器中に収納する。次
に、ユニットセル中に所定の電解液（実施例1,2、比較
例１においてはテトラブチルホスホニウムテトラフルオ
ロボレートをプロピレンカーボネートに1.0M/lの濃度で
溶解したもの、実施例3,4、比較例２においては30％硫
酸水溶液）を注入して分極性電極１、２およびセパレー
タ３中にこの電解液を充分に含浸後、ポリプロピレン製
パッキング６を介してキャップ４および缶５の端部をか
しめて封口した。The sheet-shaped electrode material is punched into a disk to form polarizable electrodes 1 and 2 (diameter 15 mm, thickness 0.6 mm). These polarizable electrodes 1 and 2 are made of stainless steel through a separator 3 made of a nonwoven fabric of polypropylene fiber. In an outer container comprising a cap 4 and a stainless steel can 5. Next, a predetermined electrolytic solution (in Examples 1 and 2 and in Comparative Example 1, tetrabutylphosphonium tetrafluoroborate was dissolved in propylene carbonate at a concentration of 1.0 M / l in the unit cells, Examples 3, 4, In Comparative Example 2, a 30% aqueous sulfuric acid solution was injected, and the electrolyte was sufficiently impregnated into the polarizable electrodes 1 and 2 and the separator 3, and the cap 4 and the end of the can 5 were closed via a polypropylene packing 6. I sealed it off.
前述のようにして作製した電気二重層コンデンサのユ
ニットセルを使用し、20℃において実施例1,2と比較例
１では2.8V、実施例3,4と比較例２では0.9Vで、それぞ
れ30分間の定電圧充電を行い、その後1mA定電流放電
し、放電時の端子間電圧がOVに至るまでの時間を測定し
て初期容量（Ｆ）を算出した。さらに、交流二端子法
（周波数1kHz）で内部抵抗を測定した。次に、同セルを
70℃において1000時間実施例1,2と比較例１では2.8V、
実施例3,4と比較例２では0.9V連続印加した後の容量を
同様にして測定し、初期値と比較して容量劣化率（％）
を算出した。以上の結果を第１表に示した。Using the unit cell of the electric double layer capacitor manufactured as described above, at 20 ° C., 2.8 V in Examples 1 and 2 and Comparative Example 1 and 0.9 V in Examples 3 and 4 and Comparative Example 2, respectively. Then, the battery was discharged at a constant current of 1 mA, and the time until the inter-terminal voltage reached OV at the time of discharging was measured to calculate the initial capacity (F). Further, the internal resistance was measured by an AC two-terminal method (frequency 1 kHz). Next, the cell
2.8 V in Examples 1 and 2 and Comparative Example 1 at 70 ° C. for 1000 hours,
In Examples 3 and 4 and Comparative Example 2, the capacitance after continuously applying 0.9 V was measured in the same manner, and compared with the initial value, the capacity deterioration rate (%)
Was calculated. The results are shown in Table 1.
［発明の効果］ 以上説明したように本発明によれば、高温条件下での
容量劣化率が低く且つ内部抵抗の増大も少ない長期信頼
性の高い電気二重層コンデンサが得られる。 [Effect of the Invention] As described above, according to the present invention, it is possible to obtain an electric double layer capacitor having a low long-term reliability with a low capacity deterioration rate under a high temperature condition and a small increase in internal resistance.
第１図は本発明による電気二重層コンデンサの一実施態
様を示す部分断面図である。 1,2……分極性電極 ３……セパレータ ４……キャップ ５……缶 ６……パッキングFIG. 1 is a partial sectional view showing an embodiment of the electric double layer capacitor according to the present invention. 1,2 ... Polarizable electrode 3 ... Separator 4 ... Cap 5 ... Can 6 ... Packing
───────────────────────────────────────────────────── フロントページの続き (72)発明者 真田 恭宏 神奈川県横浜市保土ケ谷区川島町1404― １―11 (72)発明者 有賀 広志 神奈川県横浜市神奈川区片倉１―17―14 (56)参考文献 特開 昭55−99714（ＪＰ，Ａ) 特開 昭61−66373（ＪＰ，Ａ) 特開 昭60−42809（ＪＰ，Ａ) 特開 昭59−172230（ＪＰ，Ａ) 特開 昭62−232112（ＪＰ，Ａ) ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Yasuhiro Sanada 1404-1 Kawashima-cho, Hodogaya-ku, Yokohama-shi, Kanagawa Prefecture 1-172 (72) Inventor Hiroshi Ariga 1-17-14, Katakura, Kanagawa-ku, Yokohama-shi, Kanagawa Prefecture (56) Reference Document JP-A-55-99714 (JP, A) JP-A-61-66373 (JP, A) JP-A-60-42809 (JP, A) JP-A-59-172230 (JP, A) JP-A-62 232112 (JP, A)
Claims (3)
気二重層を利用する電気二重層コンデンサにおいて、不
純物であるFeが100ppm以下、Crが5ppm以下、Niが5ppm以
下、Naが150ppm以下、Ｋが100ppm以下、Clが100ppm以下
で、灰分が0.5％以下のヤシガラ活性炭よりなる分極性
電極を用いることを特徴とする電気二重層コンデンサ。An electric double layer capacitor utilizing an electric double layer formed at the interface between a polarizable electrode and an electrolytic solution, wherein the impurities Fe are 100 ppm or less, Cr is 5 ppm or less, Ni is 5 ppm or less, and Na is 150 ppm or less. Hereinafter, an electric double layer capacitor using a polarizable electrode made of coconut shell activated carbon having K of 100 ppm or less, Cl of 100 ppm or less, and ash of 0.5% or less.
m2/g、平均細孔径が13〜20Å、全細孔容積が0.6〜0.9ml
/g、細孔径20Å以上の細孔の容積が全細孔容積に対して
30〜50％の範囲である請求項１記載の電気二重層コンデ
ンサ。2. The activated carbon of coconut shell has a specific surface area of 1500 to 1900.
m 2 / g, an average pore diameter of 13～20A, total pore volume 0.6~0.9ml
/ g, the volume of pores with a pore diameter of 20 mm or more relative to the total pore volume
2. The electric double layer capacitor according to claim 1, wherein the value is in the range of 30 to 50%.
又は２記載の電気二重層コンデンサ。3. The electrolyte according to claim 1, wherein the electrolyte is a non-aqueous solvent-based electrolyte.
Or the electric double layer capacitor according to 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63068247A JP3038676B2 (en) | 1988-03-24 | 1988-03-24 | Electric double layer capacitor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63068247A JP3038676B2 (en) | 1988-03-24 | 1988-03-24 | Electric double layer capacitor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01241811A JPH01241811A (en) | 1989-09-26 |
| JP3038676B2 true JP3038676B2 (en) | 2000-05-08 |
Family
ID=13368245
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63068247A Expired - Fee Related JP3038676B2 (en) | 1988-03-24 | 1988-03-24 | Electric double layer capacitor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3038676B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004011371A1 (en) * | 2002-07-30 | 2004-02-05 | Kuraray Chemical Co.,Ltd. | Activated carbon, method for production thereof, polarized electrode and electrical double layer capacitor |
| WO2018140367A1 (en) * | 2017-01-27 | 2018-08-02 | Cabot Corporation | Supercapacitors containing carbon black particles cleaned with an acid |
| WO2020017553A1 (en) | 2018-07-20 | 2020-01-23 | 株式会社クラレ | Carbonaceous material and method for producing same, electrode active material for electrochemical devices, electrode for electrochemical devices, and electrochemical device |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3837866B2 (en) * | 1997-10-15 | 2006-10-25 | 三菱化学株式会社 | Electric double layer capacitor |
| JP2002110472A (en) * | 2000-09-26 | 2002-04-12 | Mitsubishi Chemicals Corp | Electrical double layer capacitor |
| US7154738B2 (en) | 2002-11-29 | 2006-12-26 | Honda Motor Co., Ltd. | Polarizing electrode for electric double layer capacitor and electric double layer capacitor therewith |
| US7342770B2 (en) | 2003-07-09 | 2008-03-11 | Maxwell Technologies, Inc. | Recyclable dry particle based adhesive electrode and methods of making same |
| US7295423B1 (en) | 2003-07-09 | 2007-11-13 | Maxwell Technologies, Inc. | Dry particle based adhesive electrode and methods of making same |
| US7352558B2 (en) | 2003-07-09 | 2008-04-01 | Maxwell Technologies, Inc. | Dry particle based capacitor and methods of making same |
| EP1675141B1 (en) * | 2003-10-17 | 2018-01-03 | Power Carbon Technology Co., Ltd. | Method for producing activated carbon for electrode |
| US7227737B2 (en) | 2004-04-02 | 2007-06-05 | Maxwell Technologies, Inc. | Electrode design |
| US7245478B2 (en) * | 2004-08-16 | 2007-07-17 | Maxwell Technologies, Inc. | Enhanced breakdown voltage electrode |
| FR2886045B1 (en) * | 2005-05-23 | 2007-07-13 | Ceca Sa Sa | ELECTRODE FOR ENERGY STORAGE SYSTEMS, METHOD FOR MANUFACTURING SAME, AND ENERGY STORAGE SYSTEM COMPRISING SAME |
| JP2007194614A (en) * | 2005-12-21 | 2007-08-02 | Showa Denko Kk | Electric double layer capacitor |
| JP2007169117A (en) * | 2005-12-22 | 2007-07-05 | Nippon Oil Corp | Activated carbon and electrical double layer capacitor using same |
| WO2008053919A1 (en) * | 2006-11-02 | 2008-05-08 | Kuraray Chemical Co., Ltd | Activated carbon and process for production thereof, nonaqueous type polarizable electrodes and electric double-layer capacitors |
| TWI624980B (en) | 2016-01-22 | 2018-05-21 | Asahi Chemical Ind | Non-aqueous lithium storage battery |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6015138B2 (en) * | 1979-01-25 | 1985-04-17 | 松下電器産業株式会社 | electric double layer capacitor |
| JPS59172230A (en) * | 1983-03-18 | 1984-09-28 | 松下電器産業株式会社 | Electric double layer capacitor |
| JPS6042809A (en) * | 1983-08-18 | 1985-03-07 | 松下電器産業株式会社 | Electric double layer capacitor |
| JPS6166373A (en) * | 1984-09-07 | 1986-04-05 | Matsushita Electric Ind Co Ltd | Manufacture of polarized electrode |
| JPS62232112A (en) * | 1986-04-01 | 1987-10-12 | 旭硝子株式会社 | Electric double-layer capacitor |
-
1988
- 1988-03-24 JP JP63068247A patent/JP3038676B2/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004011371A1 (en) * | 2002-07-30 | 2004-02-05 | Kuraray Chemical Co.,Ltd. | Activated carbon, method for production thereof, polarized electrode and electrical double layer capacitor |
| US7759289B2 (en) | 2002-07-30 | 2010-07-20 | Kuraray Chemical Co., Ltd. | Activated carbon, method for production thereof, polarizing electrode and electrical double layer capacitor |
| WO2018140367A1 (en) * | 2017-01-27 | 2018-08-02 | Cabot Corporation | Supercapacitors containing carbon black particles cleaned with an acid |
| WO2020017553A1 (en) | 2018-07-20 | 2020-01-23 | 株式会社クラレ | Carbonaceous material and method for producing same, electrode active material for electrochemical devices, electrode for electrochemical devices, and electrochemical device |
| US11731880B2 (en) | 2018-07-20 | 2023-08-22 | Kuraray Co., Ltd. | Carbonaceous material and method for producing same, electrode active material for electrochemical devices, electrode for electrochemical devices, and electrochemical device |
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| Publication number | Publication date |
|---|---|
| JPH01241811A (en) | 1989-09-26 |
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