TW201142885A - Electric double layer capacitor - Google Patents
Electric double layer capacitor Download PDFInfo
- Publication number
- TW201142885A TW201142885A TW099142625A TW99142625A TW201142885A TW 201142885 A TW201142885 A TW 201142885A TW 099142625 A TW099142625 A TW 099142625A TW 99142625 A TW99142625 A TW 99142625A TW 201142885 A TW201142885 A TW 201142885A
- Authority
- TW
- Taiwan
- Prior art keywords
- electrode
- fluorine
- electric double
- double layer
- salt
- Prior art date
Links
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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
- H01G11/22—Electrodes
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
-
- 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
- H01G11/44—Raw materials therefor, e.g. resins or coal
-
- 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
-
- 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
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/60—Other road transportation technologies with climate change mitigation effect
- Y02T10/70—Energy storage systems for electromobility, e.g. batteries
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
Description
201142885 六、發明說明: 【發明所屬之技術領域】 本發明係關於雙電層電容器。 【先前技術】 雙電層電容器,因期待作爲電動汽車或瞬間停電時之 電源而有各種之探討。而對此般之雙電層電容器期望有高 靜電容量與低內部電阻,而作爲溶解電解質之溶劑,則係 使用水系之溶劑(專利文獻1)或非氟系之非水系溶劑(專利 文獻2)或氟系之非水系溶劑(專利文獻3) » 又,於非水系之溶劑中,專利文獻2中亦提案出電極 之構成’其記述具有藉由使以熔融KOH活化處理法(鹼活 化處理法)所活化之特定之粒徑與細孔容積之球狀活性碳 與導電性賦予劑與高分子系結合材成爲特定之體密度,而 可實現高靜電容量與低內部電阻。 [先前技術文獻] [專利文獻] [專利文獻1]日本特開2007-157976號公報 [專利文獻2]日本特開2001-143973號公報 [專利文獻3]國際公開第2008/084846號 【發明內容】 [發明所欲解決之課題] 雙電層電容器不僅要求上述之高靜電容量與低內部電 阻,亦同時必須要有與其相符之高耐電壓。 -5- 201142885 本發明之目的係以提供具有高靜電容量與低內部電阻 ,並且耐電壓高之雙電層電容器爲目的。 [用以解決課題之手段] 即,本發明係關於具備含有使難石墨化碳以水蒸氣活 化所得之活性碳粒子(IA)、結合材(IB)、科琴黑(1C)及丙 烯酸系化合物(ID)之電極層的雙電層電容器用電極。 本發明之電極中,前述電極層係以設置於在集電體表 面所形成之導電性被膜上爲佳。 又,電極層之電極密度係以0.45 g/cm3以下爲佳。 本發明亦係關於具備本發明之電極的雙電層電容器。 本發明之雙電層電容器係以具備非水系電解液作爲電 解液,其中亦以具備氟系電解液爲佳。 [發明之効果] 依據本發明,可提供具有高靜電容量與低內部電阻, 並且耐電壓高之雙電層電容器。 【實施方式】 本發明之雙電層電容器用電極,其特徵爲具備含有使 難石墨化碳以水蒸氣活化所得之活性碳粒子(IA)、結合材 (IB)、科琴黑(1C)及丙烯酸系化合物(ID)之電極層。以下 ,說明關於各構成。 (IA)特定之活性碳粒子 201142885 一般而言,活性碳粒子具有使雙電層電容器之靜電容 量變大之用途。本發明所使用之活性碳粒子係爲使難石墨 化碳粒子以水蒸氣活化所得之活性碳粒子。 活性碳材料雖有容易石墨化之活性碳(易石墨化碳), 與難以石墨化之活性碳(難石墨化碳),但本發明中係使用 難石墨化碳。又,爲了使活性碳粒子活性化,而有施行水 蒸氣活化處理法或熔融KOH活化處理法(鹼活化處理法)等 之活化處理,但本發明中係採用水蒸氣活化處理法。 藉由使難石墨化碳以水蒸氣活化處理所得之活性碳粒 子,在施加高電壓時下之容量劣化爲少等之特性優異,其 理由並未明朗,但此等特性在與使用易石墨化碳之情況, 或與以熔融KOH活化處理法進行活化處理之情況相比而 有所提升。 難石墨化碳係指即使在以惰性氣體環境下之進行高溫 碳化處理亦難以石墨化之碳,而可與在以相同碳化處理下 而容易石墨化之易石墨化碳有所區分。難石墨化碳一般的 而言可舉出對熱硬化性樹脂或天然有機物予以碳化處理者 ,且易石墨化碳係爲對熱可塑性樹脂或石油瀝青等予以碳 化處理者。 作爲難石墨化碳之原料的熱硬化性樹脂,例如可舉出 酚樹脂、環氧樹脂、醇酸樹脂、三聚氰胺樹脂、脲樹脂、 胺基甲酸酯樹脂、不飽和聚酯樹脂、酞酸二烯丙酯樹脂等 之外,尙可舉出糠醛樹脂、聚矽氧樹脂、呋喃樹脂、茬樹 脂等,藉由將粒狀之材料予以碳化處理而可得到活性碳粒 子。 201142885 作爲難石墨化碳之原料的天然有機物,以天然椰殻由 可取得之容易度之觀點爲佳,並藉由對不含有有害雜質者 進行碳化處理而可得到椰殼碳。 該難石墨化碳之水蒸氣活化處理係以以往公知之方法 即可,例如可例示於水蒸氣環境下,使難石墨化碳以較佳 爲5 00〜100(TC,更佳爲700〜1 000°C之溫度進行約5分間 〜1 0小時處理之方法,但並非係受此條件所限定者。經水 蒸氣活化處理所得之活性碳粒子,因其進行多孔質化而進 而被活性化。 經水蒸氣活化處理之活性碳粒子,由可得到大容量且 低內部電阻之雙電層電容器的觀點,以平均粒徑爲20 μηι 以下,較佳爲ΙΟμηι以下,並以比表面積爲1 5 00〜3 000 m2/g之活性碳粒子爲佳。又,以萃取法所測定之鉀含有量 爲0〜200PPm程度,或細孔容積爲1.5cm3/g以下之活性 碳粒子亦爲佳。 源自椰殼碳之經水蒸氣活化處理之難石墨化碳活性碳 粒子之市售品,例如可例示KURARAY CHEMICAL(股)製 之 YP50F、YP50FH、YP80F、YP80FH(皆爲商品名)等,但 不受此等所限定者》 又,作爲難石墨化碳之原料之有機物,亦可舉出酚樹 脂。源自酚樹脂之經水蒸氣活化處理之難石墨化碳活性碳 粒子之市售品,例如可例示KURARAY CHEMICAL(股)製 之RP-2 0(商品名)等,但不受此等所限定者。 (IB)結合材 201142885 結合材(IB)係在使用活性碳粒子(〗A)、及作爲導電材 而添加之科琴黑(1C)等之其他電極成分進行成形爲電極時 ’用以使彼等粒子結合所使用者。 故’只要係可達成目的者則無特別限定,通常使用聚 四氟乙嫌(PTFE)、聚偏二氟乙烯(PVdF)等之氟系樹脂;丁 二烯橡膠、苯乙烯丁二烯橡膠等之非氟系彈性體。 其中’由耐電壓性良好之觀點,以氟系樹脂,特別係 以P T F E爲佳,但其與集電體之密著性差,而會使加工性 或長期信賴性下降。因此,由耐壓性良好且與集電體之密 著性爲良好之觀點’以非氟系彈性體之丙烯酸酯系共聚物 爲佳。 (1C)科琴黑 本發明中,科琴黑(1C)係作用作爲導電材。作爲電容 器之電極材料之導電材,係爲大比表面積之不活性碳,且 具有賦予電子傳導性之作用,除科琴黑之外,例如亦已知 有碳黑、乙炔黑 '天然石墨、人造石墨等之碳質材料;金 屬纖維、導電性氧化鈦、氧化釕等之無機材料,在使用將 難石墨化碳以水蒸氣活化處理所得之活性碳粒子(IA)時, 藉由倂用科琴黑(1C),可賦予更高之耐電壓,並具有高靜 電容量與低內部電阻。 科琴黑(1C)之市售品,可舉出例如LION(股)製之碳 ECP600JD 。 (ID)丙烯酸系化合物 201142885 製作電極時,使活性碳粒子(ΙΑ)、結合材(IB)、科琴 黒(1C)、其他因應必要所添加之其他添加劑分散於溶劑, 例如分散於水中作成漿體,塗布於金屬箔或集電體上而成 形。此時,使粒子均質地分散於漿體中,且爲了將流動性 調整爲適當之流動性,而添加增黏劑。由於此增黏劑成分 亦殘留於電極中,除會對靜電容量、內部電阻,同時亦爲 會耐電壓產生影響。 本發明中,丙烯酸系化合物(ID)係作爲此般之增黏劑 ,加上活性碳粒子(IA)、結合材(IB)及科琴黑(1C)而所添 加之成分,意外地,與作爲增黏劑而公知之其他化合物, 例如羧基甲基纖維素(CMC)等相比,其耐電壓爲高,在對 使用具有高耐電壓之氟系電解液之電容器之性能提升產生 較大作用。其理由雖未明朗,推定其一個原因係由於並非 係具有比較容易被氧化之羥基而係具有不容易被氧化之羧 基之故。當然地,作爲原來添加目的之其他之粒子之分散 性亦爲良好,所製作之電極之強度亦爲良好。 丙烯酸系化合物(ID)係包含聚丙烯酸或其鈉或鉀、鋰 等之鹽;聚丙烯酸鹽、聚丙烯酸酯、丙烯酸共聚物等之1 種或2種以上,具體而言,可舉出例如聚丙烯酸;丙烯酸 甲酯、丙烯酸乙酯、丙烯酸丙酯、丙烯酸丁酯、丙烯酸異 丙酯等之丙烯酸酯之單獨聚合物或共聚物等。 丙烯酸系化合物之市售品,例如可例示東亞合成(股) 製之Aron A-10H等之聚丙烯酸·,東亞合成(股)製之Aron A-30等之聚丙烯酸銨。 -10 - 201142885 (IE)其他電極成分 除以上之活性碳粒子(ΙΑ)、結合材(IB)、科琴黑(IC) 及丙烯酸系化合物(ID),亦可配合雙電層電容器用之電極 通常所配合之添加劑。而其他添加劑,例如可舉出科琴黑 (1C)以外之上述導電材。 理想之添加劑,例如可舉出乙炔黑,市售品可舉出例 如電氣化學工業(股)製之DenkaBlackFX-35。 此等電極成分係相對於活性碳粒子(IA)100質量份, 以配合結合材(IB)2〜20質量份、科琴黑(IC)1〜30質量份 、丙烯酸系化合物(ID)1〜5質量份爲佳。爲了得到更高靜 電容量與更低內部電阻與更高耐電壓,相對於活性碳粒子 (IA)100質量份,以配合結合材(iB)3〜10質量份、科琴黑 (IC) 8〜20質量份、丙烯酸系化合物(ID)2〜4質量份爲更 佳。 在配合其他電極成分(IE)時,係相對於活性碳粒子 (IA) 100質量份,爲50質量份以下,更佳爲10質量份以 下。其下限係爲可達成作爲配合目的之量。 在配合例如科琴黑(1C)與其他導電材時,爲可得到良 好導電性(低內部電阻),且若過多時由於電容器之靜電容 量減少,而在與活性碳粒子(IA)之合計量中,以調整科琴 黑(1C)與其他導電材之合計量成爲1〜50質量%爲佳。 電極可用各種方法形成。例如,將活性碳粒子(IA)、 科琴黑(1C)及因應必要之其他電極成分(IE),例如其他導 電材予以乾式混合。以其他混合過程將丙烯酸系化合物 (ID) 與水適宜地添加並使粒子分散。其次,適宜添加結合 -11 - 201142885 材(IB)與水後進行濕式混合,而調製成均質之電極形成用 之漿體。將此漿體塗布於集電體等之金屬箔上,適宜加壓 ,並乾燥而製作成電極。 本發明中所製作之電極之體密度(電極密度)係以調整 至0.45g/cm1 2以下爲佳。 由提升靜電容量或降低內部電阻之觀點,已知有使電 極密度高密度化(〇.6g/cm2以上)一事(例如專利文獻2),但 由電容器之耐電壓之觀點,尙未有檢討關於電極密度之事 例。 電極密度,由耐電壓良好之觀點以〇.45g/cm2以下爲 佳,更佳爲〇.40g/cm2以下。另一方面,由維持機械性強 度之觀點,以0.35g/cm2以上爲佳。 調整電極密度之方法並無特別限定,例如可採用以下 之方法。 (1) 調節電極用漿體之固形分濃度之方法 例如,較佳以調整固形分濃度至1 5〜2 5質量%,更佳 爲1 8〜2 2質量%。 -12- 1 於塗布後調節加壓電極用漿體之塗膜時之壓力的方法 2 加壓壓力只要配合目的之電極厚等適宜選定即可。 此等之方法可單獨或予以組合進行。 集電體只要係具有對化學性、電化學之耐蝕性者即可 。以活性碳爲主體之極化電極之集電體,較佳可使用不鏽 鋼、鋁、鈦或鉬。此等之中,以不鏽鋼或鋁,在所得之雙 201142885 電層電容器之特性與價格之雙面中爲特佳之材料。 集電體爲了可在高電壓下且安定地使用,以形成導電 性被膜爲佳。導電性被膜係爲將作爲塡料之平均粒子徑 ΙΟμιη之石墨粒子、作爲黏合劑之纖維素之水塗料塗布於 集電體上者,而膜厚係以1〜30μηι之厚度爲佳。藉由作成 此厚度,電極層之形成變得容易,且可同使抑制電極內部 電阻之增強。 由提升電極之耐電壓、高溫負荷特性等良好之觀點, 本發明之電極係以在形成有導電性被膜之集電體之導電性 被膜上形成電極層爲佳。 電極係可使用上述之電極作爲兩極而作成雙電層電容 器,在單側使用非極化電極之構成,例如,將以金屬酸化 物等之電池活物質爲主體之正極,與以活性碳爲主體之本 發明之電極之負極予以組合之構成亦可。 本發明又亦係關於具備本發明之電極之雙電層電容器 〇 本發明之雙電層電容器之構造,除具備本發明之電極 以外,可與以往公知之雙電層電容器相同,在正極與負極 之間可經由因應需要之間隔器塡充電解液而構成。 電解液可爲水系電解液,但由可擴大動作電壓之觀點 ’以非水系(有機系)電解液爲佳。 本發明中適宜使用之非水系電解液爲氟系電解液,其 包含氟系溶劑(ΙΙΑ)與電解質鹽(ΙΙΒ)。 (ΙΙΑ)氟系溶劑 -13- 201142885 本發明之雙電層電容器所用之氟系溶劑(ΠΑ),例如以 專利文獻3記載之含有含氟環狀碳酸鹽之氟系溶劑,由高 耐電性與大幅電解質溶解性優良之觀點而爲佳。 含氟環狀碳酸鹽,以含有式(1): 化 〇=c b.201142885 VI. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to an electric double layer capacitor. [Prior Art] Electric double layer capacitors are expected to be discussed as electric power sources or power sources in the event of an instantaneous power failure. In this case, an electric double layer capacitor is expected to have a high electrostatic capacity and a low internal resistance, and a solvent for dissolving the electrolyte is a water-based solvent (Patent Document 1) or a non-fluorine-based non-aqueous solvent (Patent Document 2). Or a fluorine-based non-aqueous solvent (Patent Document 3). Further, in the non-aqueous solvent, Patent Document 2 also proposes a structure of an electrode, which has a method of activating the molten KOH (alkali activation treatment). The spherical activated carbon and the conductivity imparting agent and the polymer binder which are activated by the specific particle diameter and the pore volume have a specific bulk density, and a high electrostatic capacity and a low internal resistance can be realized. [PRIOR ART DOCUMENT] [Patent Document 1] JP-A-2007-157976 (Patent Document 2) JP-A-2001-143973 (Patent Document 3) International Publication No. 2008/084846 [The problem to be solved by the invention] The electric double layer capacitor requires not only the above-mentioned high electrostatic capacity and low internal resistance, but also a high withstand voltage corresponding thereto. -5- 201142885 The object of the present invention is to provide an electric double layer capacitor having a high electrostatic capacity and a low internal resistance and having a high withstand voltage. [Means for Solving the Problem] The present invention relates to an activated carbon particle (IA), a binder (IB), a Ketjen black (1C), and an acrylic compound which are obtained by activating water vapor of non-graphitizable carbon. An electrode for an electric double layer capacitor of an electrode layer of (ID). In the electrode of the present invention, the electrode layer is preferably provided on the conductive film formed on the surface of the current collector. Further, the electrode layer has an electrode density of 0.45 g/cm3 or less. The present invention also relates to an electric double layer capacitor comprising the electrode of the present invention. The electric double layer capacitor of the present invention is preferably provided with a nonaqueous electrolytic solution as the electrolytic solution, and preferably a fluorine-based electrolytic solution. [Effect of the Invention] According to the present invention, an electric double layer capacitor having a high electrostatic capacity and a low internal resistance and having a high withstand voltage can be provided. [Embodiment] The electrode for an electric double layer capacitor of the present invention is characterized by comprising activated carbon particles (IA), a binder (IB), and Ketjen black (1C) obtained by activating water vapor of non-graphitizable carbon. An electrode layer of an acrylic compound (ID). Hereinafter, each configuration will be described. (IA) Specific activated carbon particles 201142885 In general, activated carbon particles have a function of increasing the electrostatic capacitance of an electric double layer capacitor. The activated carbon particles used in the present invention are activated carbon particles obtained by activating water vapor of non-graphitizable carbon particles. The activated carbon material has activated carbon (e.g., graphitizable carbon) which is easily graphitized, and activated carbon (hardly graphitizable carbon) which is difficult to graphitize. However, in the present invention, non-graphitizable carbon is used. Further, in order to activate the activated carbon particles, an activation treatment such as a steam activation treatment method or a molten KOH activation treatment method (alkali activation treatment method) may be employed. However, in the present invention, a steam activation treatment method is employed. The activated carbon particles obtained by activating the hardly graphitizable carbon by steam activation are excellent in characteristics such as a decrease in capacity when a high voltage is applied, and the reason is not clear. However, these characteristics are easy to graphitize and use. The case of carbon is improved as compared with the case of activation treatment by the molten KOH activation treatment. The non-graphitizable carbon refers to carbon which is difficult to graphitize even when subjected to high-temperature carbonization in an inert gas atmosphere, and can be distinguished from easily graphitizable carbon which is easily graphitized by the same carbonization treatment. The non-graphitizable carbon is generally one in which a thermosetting resin or a natural organic substance is carbonized, and the easily graphitizable carbon is a carbonized thermoplastic resin or petroleum pitch. Examples of the thermosetting resin which is a raw material of the non-graphitizable carbon include a phenol resin, an epoxy resin, an alkyd resin, a melamine resin, a urea resin, a urethane resin, an unsaturated polyester resin, and a decanoic acid. In addition to the allyl ester resin and the like, a fluorene resin, a polyoxyxylene resin, a furan resin, a fluorene resin, or the like can be given, and activated carbon particles can be obtained by carbonizing the granular material. 201142885 Natural organic matter, which is a raw material for hardly graphitizable carbon, is preferred from the viewpoint of ease of availability of natural coconut shells, and coconut shell carbon can be obtained by carbonizing a person who does not contain harmful impurities. The water vapor activation treatment of the non-graphitizable carbon may be a conventionally known method, and for example, it may be exemplified in a water vapor atmosphere, and the non-graphitizable carbon is preferably 500 to 100 (TC, more preferably 700 to 1). The method of treating at a temperature of 000 ° C for about 5 minutes to 10 hours is not limited by the above conditions. The activated carbon particles obtained by the steam activation treatment are further activated by being porous. The activated carbon particles subjected to steam activation treatment have an average particle diameter of 20 μηι or less, preferably ΙΟμηι or less, and a specific surface area of 1 500, from the viewpoint of obtaining an electric double layer capacitor having a large capacity and a low internal resistance. It is preferable that the activated carbon particles are not more than 3,000 m 2 /g, and the amount of potassium measured by the extraction method is about 0 to 200 ppm, or the activated carbon particles having a pore volume of 1.5 cm 3 /g or less are also preferable. For example, YP50F, YP50FH, YP80F, and YP80FH (all trade names) manufactured by KURARAY CHEMICAL Co., Ltd., etc., may be exemplified, but are not, for example, commercially available products of the non-graphitizable carbon-activated carbon particles of the coconut shell carbon. These limited persons" A commercially available product of a non-graphitizable carbon activated carbon particle which is subjected to steam activation treatment of a phenol resin, for example, an RP made by KURARAY CHEMICAL Co., Ltd., may be used as the phenol resin. -2 0 (trade name), etc., but not limited by them. (IB) Bonding material 201142885 Bonding material (IB) is based on the use of activated carbon particles (A) and Ketjen black added as a conductive material. When the other electrode components (1C) and the like are formed into electrodes, they are used to bind the particles to the user. Therefore, as long as the object can be achieved, there is no particular limitation, and polytetrafluoroethylene (PTFE) is usually used. a fluorine-based resin such as vinylidene fluoride (PVdF); a non-fluorine-based elastomer such as butadiene rubber or styrene-butadiene rubber. Among them, a fluorine-based resin is particularly useful from the viewpoint of good withstand voltage. PTFE is preferred, but the adhesion to the current collector is poor, and the workability or long-term reliability is lowered. Therefore, the pressure resistance is good and the adhesion to the current collector is good. An elastomeric acrylate copolymer is preferred. (1C) In the present invention, Ketjen Black (1C) functions as a conductive material. The conductive material which is an electrode material of a capacitor is an inactive carbon having a large specific surface area and has an effect of imparting electron conductivity, except for Ketchen Black. Further, for example, carbonaceous materials such as carbon black, acetylene black 'natural graphite, artificial graphite, and the like; metal materials such as metal fibers, conductive titanium oxide, and cerium oxide are known, and water-vapor is activated by using non-graphitizable carbon. When the obtained activated carbon particles (IA) are treated, a higher withstand voltage can be imparted by using Ketjen black (1C), and a high electrostatic capacity and a low internal resistance are obtained. As a commercial item of Ketchen Black (1C), for example, carbon ECP600JD manufactured by LION Co., Ltd. can be cited. (ID) Acrylic Compound 201142885 When the electrode is produced, the activated carbon particles (ΙΑ), the binder (IB), the Ketjen (1C), and other additives added as necessary are dispersed in a solvent, for example, dispersed in water to form a slurry. The body is formed by coating on a metal foil or a current collector. At this time, the particles are uniformly dispersed in the slurry, and a tackifier is added in order to adjust the fluidity to an appropriate fluidity. Since the tackifier component remains in the electrode, it has an effect on the electrostatic capacity, the internal resistance, and the withstand voltage. In the present invention, the acrylic compound (ID) is a tackifier as described above, and the components added by the activated carbon particles (IA), the binder (IB), and the ketjen black (1C) are unexpectedly added. Other compounds known as tackifiers, such as carboxymethyl cellulose (CMC), have a high withstand voltage, and have a large effect on the performance improvement of a capacitor using a fluorine-based electrolyte having a high withstand voltage. . Although the reason for this is not clear, it is presumed that one of the reasons is that it is not a carboxyl group which is relatively easily oxidized and has a carboxyl group which is not easily oxidized. Of course, the dispersibility of the other particles which were originally added was also good, and the strength of the produced electrode was also good. The acrylic compound (ID) is a polyacrylic acid or a salt thereof such as sodium or potassium or lithium, or a polyacrylic acid salt, a polyacrylate or an acrylic copolymer, and the like. Specifically, for example, poly Acrylic acid; a single polymer or copolymer of acrylate such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate or isopropyl acrylate. The commercially available product of the acrylic compound is, for example, polyacrylic acid such as Aron A-10H manufactured by Toagos Co., Ltd., and ammonium polyacrylate such as Aron A-30 manufactured by Toagosei Co., Ltd. -10 - 201142885 (IE) Other electrode components in addition to the above activated carbon particles (ΙΑ), binder (IB), Ketjen black (IC) and acrylic compound (ID), can also be used with electrodes for electric double layer capacitors Additives usually formulated. Further, the other additives may, for example, be the above-mentioned conductive materials other than Ketjen black (1C). An ideal additive is, for example, acetylene black, and a commercially available product is, for example, Denka BlackFX-35 manufactured by Electric Chemical Industry Co., Ltd. The electrode component is used in an amount of 2 parts by mass to 20 parts by mass of the binder (IB), 1 to 30 parts by mass of Ketjen black (IC), and an acrylic compound (ID) 1 to 100 parts by mass of the activated carbon particles (IA). 5 parts by mass is preferred. In order to obtain higher electrostatic capacity and lower internal resistance and higher withstand voltage, with respect to 100 parts by mass of activated carbon particles (IA), 3 to 10 parts by mass of the bonding material (iB), Ketjen black (IC) 8~ 20 parts by mass and 2 to 4 parts by mass of the acrylic compound (ID) are more preferable. In the case of the other electrode component (IE), it is 50 parts by mass or less, more preferably 10 parts by mass or less, based on 100 parts by mass of the activated carbon particles (IA). The lower limit is an amount that can be achieved for the purpose of cooperation. In the case of, for example, Ketchen Black (1C) and other conductive materials, good electrical conductivity (low internal resistance) can be obtained, and if too much, the capacitance of the capacitor is reduced, and the total amount of activated carbon particles (IA) is combined. In order to adjust the total amount of Ketjen black (1C) and other conductive materials, it is preferably 1 to 50% by mass. The electrodes can be formed in a variety of ways. For example, activated carbon particles (IA), Ketjen black (1C), and other electrode components (IE) necessary for the reaction, such as other conductive materials, are dry-mixed. The acrylic compound (ID) and water are suitably added and dispersed in the other mixing process. Next, it is suitable to add a mixture of -11 - 201142885 (IB) and water, followed by wet mixing to prepare a homogeneous slurry for electrode formation. This slurry is applied onto a metal foil such as a current collector, and is suitably pressed and dried to prepare an electrode. The bulk density (electrode density) of the electrode produced in the present invention is preferably adjusted to 0.45 g/cm 2 or less. From the viewpoint of increasing the electrostatic capacitance or lowering the internal resistance, it is known that the electrode density is increased (〇6 g/cm 2 or more) (for example, Patent Document 2), but from the viewpoint of the withstand voltage of the capacitor, there is no review about An example of electrode density. The electrode density is preferably 4545 g/cm2 or less, more preferably 4040 g/cm2 or less, from the viewpoint of good withstand voltage. On the other hand, from the viewpoint of maintaining mechanical strength, it is preferably 0.35 g/cm2 or more. The method of adjusting the electrode density is not particularly limited, and for example, the following method can be employed. (1) The method of adjusting the solid content concentration of the slurry for the electrode. For example, it is preferred to adjust the solid content concentration to 15 to 25 mass%, more preferably 18 to 22 mass%. -12- 1 Method of adjusting the pressure at the time of coating the film for the slurry for pressurization after application 2 The pressurizing pressure may be appropriately selected in accordance with the electrode thickness of the purpose. These methods can be carried out either singly or in combination. The current collector may be any one that has chemical or electrochemical corrosion resistance. As the current collector of the polarized electrode mainly composed of activated carbon, stainless steel, aluminum, titanium or molybdenum can be preferably used. Among these, stainless steel or aluminum is the best material on both sides of the characteristics and price of the obtained 201142885 electric layer capacitor. The current collector is preferably formed to form a conductive film in order to be used stably at a high voltage. The conductive film is a method in which graphite particles having an average particle diameter of 塡μηη and a water-based coating of cellulose as a binder are applied to a current collector, and the film thickness is preferably 1 to 30 μm. By making this thickness, the formation of the electrode layer becomes easy, and the internal resistance of the electrode can be suppressed. The electrode of the present invention is preferably formed by forming an electrode layer on the conductive film on which the current collector of the conductive film is formed, from the viewpoint of the withstand voltage of the lift electrode and the high-temperature load characteristics. The electrode system can be an electric double layer capacitor using the above-mentioned electrode as a double pole, and a non-polarized electrode can be used on one side, for example, a positive electrode mainly composed of a battery active material such as a metal acidate, and activated carbon as a main component. The negative electrode of the electrode of the present invention may be combined. Further, the present invention relates to an electric double layer capacitor comprising the electrode of the present invention. The electric double layer capacitor of the present invention has the same structure as the conventionally known electric double layer capacitor, in addition to the electrode of the present invention, in the positive electrode and the negative electrode. The electrolyte can be formed by interposing an electrolyte according to a spacer required. The electrolytic solution may be an aqueous electrolytic solution, but a non-aqueous (organic) electrolytic solution is preferred from the viewpoint of expanding the operating voltage. The nonaqueous electrolytic solution suitably used in the present invention is a fluorine-based electrolytic solution containing a fluorine-based solvent and an electrolyte salt. (ΙΙΑ) Fluorine-based solvent-13-201142885 The fluorine-based solvent used in the electric double layer capacitor of the present invention is, for example, a fluorine-based solvent containing a fluorine-containing cyclic carbonate described in Patent Document 3, and has high electric resistance and It is preferable that the electrolyte solubility is excellent. Fluorine-containing cyclic carbonate to contain formula (1): 〇=c b.
XX
ό 2 X 4 X 3 X ό (式中,X1〜X4爲相同或相異,皆爲-Η、-F、-CF3 ' -CHF2 、-CH2F、-C2F5 或- CH2CF3;但,X1 〜X4 之至少 1 個爲-F 、-CF3、-C2F5或-CH2CF3)所示之含氟環狀碳酸鹽之溶劑 ,由靜電容量爲大,耐電壓亦高之觀點爲爲佳。 前述氟系溶劑(ΠA)中所含之含氟環狀碳酸鹽,由可特 別發揮高介電率、高耐電壓之優異特性之觀點,及由其他 電解質鹽之溶解性、內部電阻下降良好之觀點,並由提升 作爲本發明中之雙電層電容器之特性之觀點, 1ό 2 X 4 X 3 X ό (wherein, X1 to X4 are the same or different, and are all -Η, -F, -CF3' -CHF2, -CH2F, -C2F5 or -CH2CF3; however, X1 to X4 The solvent of the fluorine-containing cyclic carbonate represented by at least one of -F, -CF3, -C2F5 or -CH2CF3) is preferably a viewpoint of a large electrostatic capacity and a high withstand voltage. The fluorine-containing cyclic carbonate contained in the fluorine-based solvent (ΠA) is excellent in solubility and other internal electrolyte resistance from the viewpoint of exhibiting excellent characteristics of high dielectric constant and high withstand voltage. Point of view, and by enhancing the viewpoint of the characteristics of the electric double layer capacitor in the present invention, 1
OMHC o=c 3 FcOMHC o=c 3 Fc
d——c H H b——c ό-c H 1 2 Hc - 3 Fc Η bIc -14- 201142885D——c H H b——c ό-c H 1 2 Hc - 3 Fc Η bIc -14- 201142885
CF3-FC-CH2 FHC-CH2 、CF3-FC-CH2 FHC-CH2,
F2C-CH2 及 FHC-CHF 、 以選自上述所成群之至少1種爲佳。 含氟環狀碳酸鹽之氟含有率,由介電率、耐氧化性之 觀點,以15〜55質量%爲佳,17〜44質量%爲更佳。 其他含氟環狀碳酸鹽亦可使用如以下等。 b31 o = c o = c Ό — c H - 5 F 2cF2C-CH2 and FHC-CHF are preferably at least one selected from the group consisting of the above. The fluorine content of the fluorine-containing cyclic carbonate is preferably 15 to 55 mass%, more preferably 17 to 44 mass%, from the viewpoint of dielectric constant and oxidation resistance. Other fluorine-containing cyclic carbonates can also be used, for example, the following. B31 o = c o = c Ό — c H - 5 F 2c
2 F ό——c F H-o——c OMnc2 F ό——c F H-o——c OMnc
onMConMC
2 F ό-c ό——c F I 3 Fc b — c2 F ό-c ό——c F I 3 Fc b — c
2 F -15- 201142885 onnc2 F -15- 201142885 onnc
OUMCOUMC
〇 I 〇 I 〇 I I ch2 I chf2-hc — I CH ο〇 I 〇 I 〇 I I ch2 I chf2-hc — I CH ο
I ch2f-hc- 氟系溶劑(πa)中之含氟環狀碳酸鹽之含有率’由介電 率或黏性爲良好之觀點,以1〇〇〜2〇體積%爲佳’ 90〜20 體積%爲更佳。 溶劑(IIA)可單獨使用式(1)所示之含氟環狀碳酸鹽’ 亦可使用與其他含氟電解質鹽溶解用溶劑或非氟系電解質 鹽溶解用溶劑之混合物。又,含氟環狀碳酸鹽—般而言由 於熔點爲髙,單獨存在時有對在低溫之動作產生障礙之情 況。在此般情況時,由使耐氧化性、黏性提升’維持低溫 特性之觀點,以使用式(1)所示之含氟環狀碳酸鹽與其他含 氣電解質鹽溶解用溶劑之混合物爲佳。 作爲式(1)所示之含氟環狀碳酸鹽之共溶劑所使用之含 氟電解質鹽溶解用溶劑,可舉出含氟鏈狀碳酸鹽、含氟鏈 狀酯、含氟鏈狀醚、含氟內酯、含氟環丁碾衍生物等。 含氟鏈狀碳酸鹽,由黏性或耐氧化性爲良好之觀點, 以式(2): [化4] Ο (2) 4之烷基或碳I ch2f-hc- The content rate of the fluorine-containing cyclic carbonate in the fluorine-based solvent (πa) is preferably from 1 to 2% by volume from the viewpoint of good dielectric constant or viscosity. The volume % is more preferred. The solvent (IIA) may be a fluorine-containing cyclic carbonate represented by the formula (1), or a mixture with another solvent for dissolving the fluorine-containing electrolyte salt or a solvent for dissolving the non-fluorine-based electrolyte salt. Further, the fluorine-containing cyclic carbonate generally has a melting point of ruthenium, and when it exists alone, it may cause an obstacle to the action at a low temperature. In such a case, it is preferred to use a mixture of a fluorine-containing cyclic carbonate represented by the formula (1) and another solvent for dissolving the gas-containing electrolyte salt from the viewpoint of improving oxidation resistance and viscosity. . Examples of the solvent for dissolving the fluorine-containing electrolyte salt used in the co-solvent of the fluorine-containing cyclic carbonate represented by the formula (1) include a fluorine-containing chain carbonate, a fluorine-containing chain ester, and a fluorine-containing chain ether. Fluorine-containing lactone, fluorine-containing cyclobutyl derivative, and the like. Fluorinated chain carbonate, from the viewpoint of good adhesion or oxidation resistance, with the formula (2): [Chemical 4] Ο (2) 4 alkyl or carbon
II R f “一O-C-O-R f (式中,Rfal及Rfa2爲相同或相異之碳數 -16- 201142885 數1〜4之含氟烷基。但,至少一者爲: 基)所示者爲佳。 含氟鏈狀碳酸鹽之中,由可特別勇 電壓之優異特性之觀點,及由其他電解 低內部電阻且可維持低溫特性之觀點, 明中之雙電層電容器之特性之觀點,以 [化5] ΟII R f "-OCOR f (wherein, Rfal and Rfa2 are the same or different carbon number -16 - 201142885 number 1 to 4 of the fluorine-containing alkyl group. However, at least one is: base) is better Among the fluorine-containing chain carbonates, from the viewpoint of the excellent characteristics of the voltage which can be particularly strong, and the viewpoint of the characteristics of the electric double layer capacitors from the viewpoint of other electrolysis and low internal resistance and maintaining low-temperature characteristics, 5] Ο
HCF2CF2CH2-〇-i-〇-CH2C ΟHCF2CF2CH2-〇-i-〇-CH2C Ο
II CF 3CF2CH2 —〇 — C — Ο — CH2CF; ΟII CF 3CF2CH2 —〇 — C — Ο — CH2CF; Ο
II CF 3CH2 — 〇 — C — 〇—CH2CF3 0II CF 3CH2 — 〇 — C — 〇—CH2CF3 0
II cf3 — 〇—C — 〇 — CF3 ?Fs ? V3 cf3ch-o-c-o-chcf3 其他含氟鏈狀碳酸鹽可使用如下述 炭數1〜4之含氣院 揮高介電率、高耐 質鹽之溶解性、減 並由提升作爲本發 下述等爲佳。 f2cf2h iCFa 、 等。 -17- 201142885 [its] οII cf3 — 〇—C — 〇—CF3 ?Fs ? V3 cf3ch-oco-chcf3 Other fluorine-containing chain carbonates can be used in the gas-filled high-potency, high-resistance salt, such as the following carbon numbers 1 to 4. The solubility and the reduction are preferably as follows. F2cf2h iCFa, and so on. -17- 201142885 [its] ο
II hcf2cf2ch2-o-c-o-ch3 、 ο hcf2cf2ch2-o-c-o-ch2ch3 οII hcf2cf2ch2-o-c-o-ch3, ο hcf2cf2ch2-o-c-o-ch2ch3 ο
II CF3CF2CH2 — 0-0 一O - CH3 、 οII CF3CF2CH2 — 0-0 A O - CH3 , ο
II CF3CF2CH2-〇-C-〇-CH2CH3 ?F3 ? CF3CH-0-C-0-CH3II CF3CF2CH2-〇-C-〇-CH2CH3 ?F3 ? CF3CH-0-C-0-CH3
c f3 O ! II CF3CH-〇-C-〇-CH2CH3 oc f3 O ! II CF3CH-〇-C-〇-CH2CH3 o
II CF3CH2-〇-C~〇-CH2CH3 oII CF3CH2-〇-C~〇-CH2CH3 o
II cf3ch2-o-c-〇-ch3 又’例如亦可舉出日本特開平〇6_n992號公報、曰 本特開2000-327634戚公報、日本特開2〇〇1256983號公 報等中記載之化合物。 其中,由耐氧化性、電解質鹽之溶解性爲良好之觀點 ’以下述者爲佳。 -18- 201142885 [化7] ΟFor example, the compound described in Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Among them, the oxidation resistance and the solubility of the electrolyte salt are good, and the following are preferred. -18- 201142885 [化7] Ο
II CF3CF2CH2-〇-C-〇-CH2CF2CF3 οII CF3CF2CH2-〇-C-〇-CH2CF2CF3 ο
II cf3ch2—Ο—C—ο—ch2cf3 、 οII cf3ch2—Ο—C—ο—ch2cf3 , ο
II HCF2CF 2〇Η2 一Ο 一C一〇一CH3 οII HCF2CF 2〇Η2 一Ο一一一一一CH3 ο
II HCF2CF2CH2 - Ο - C - Ο - CH2CH3 、 Ο CF3CF2CH2-〇-C-〇一CH3 \ oII HCF2CF2CH2 - Ο - C - Ο - CH2CH3 , Ο CF3CF2CH2-〇-C-〇一CH3 \ o
II cf3ch2-o-c-o-ch2ch3 、 oII cf3ch2-o-c-o-ch2ch3 , o
II cf3ch2-o-c-o-ch3 號公報 026015 200 1 - 記載之 宜沸點 含氟鏈狀醚例如可舉出日本特開平〇8_〇37〇24 、日本特開平09-097627號公報、日本特開平j ! 號公報、日本特開2000-29428 1號公報、日本特開 052737號公報、日本特開平11-307123號公報等中 化合物。 其中’由與其他溶劑之相溶性爲良好且具有適 之觀點’以式(3 ):(2) cf. The compound of the Japanese Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. Wherein 'the compatibility with other solvents is good and has a suitable viewpoint' to formula (3):
Rfcl-0-Rfc2 (3) 之含氟 (式中’ Rfel及Rf。2爲相同或相異,皆爲碳數2〜4 -19- 201142885 院基)所示之含氟鏈狀醚爲佳。 特別係,Rfcl 可舉出例如、-CH2CF2CHF2、-ch2c2f4chf2 、-CH2CF3 ' -CH2C3F6CHF2 > -CH2C2F5、-ch2cf2chfcf3 、-ch2cf(cf3)cf2chf2、-c2h4c2f5、-c2h4cf3 等,又, Rfc2 例如以-cf2cf2h、-cf2chfcf3、-c2f4chf2 ' -c2h4cf3 、-CH2CHFCF3、-C2H4C2F5 爲佳。 含氟鏈狀酯,由難燃性高,且與其他溶劑之相溶性或 耐氧化性爲良好之觀點,以式(4)=Fluorine-containing chain ethers of Rfcl-0-Rfc2 (3) (wherein Rfel and Rf. 2 are the same or different, both of which are carbon number 2 to 4 -19- 201142885) . In particular, Rfcl may be, for example, -CH2CF2CHF2, -ch2c2f4chf2, -CH2CF3'-CH2C3F6CHF2 > -CH2C2F5, -ch2cf2chfcf3, -ch2cf(cf3)cf2chf2, -c2h4c2f5, -c2h4cf3, etc. Further, Rfc2 is, for example, -cf2cf2h, -cf2chfcf3, -c2f4chf2 ' -c2h4cf3, -CH2CHFCF3, -C2H4C2F5 are preferred. The fluorine-containing chain ester has high flame retardancy and good compatibility with other solvents or oxidation resistance, and is expressed by the formula (4)=
R R Iο 1o=c (式中,Rfbl及Rfb2爲相同或相異,皆爲碳數1〜4之含氟 烷基)所示者爲佳。 含氟鏈狀酯例如可舉出cf3c(=o)oc2f5、cf3c(=o)och2cf3 、CF3C( = o)och2ch2cf3、CF3C( = 0)0CH2C2F5、 CF3C( = 0)0CH2CF2CF2H、 CF3C( = 0)0CH(CF3)2 ' CF3C(= o)och(cf3)2等,其中,由與其他溶劑之相溶性 、黏性、耐氧化性等爲良好之觀點,以cf3c(= 〇)〇c2f5 、CF3C( = 0)0CH2C2F5 、 CF3C(= o)och2cf2cf2h 、 CF3C(=0)0CH2CF3、CF3C(=0)0CH(CF3)2 爲特佳。 含氟內酯例如可舉出式(5): -20- 201142885R R Iο 1o = c (wherein, Rfbl and Rfb2 are the same or different, and all are fluorine-containing alkyl groups having 1 to 4 carbon atoms) are preferred. Examples of the fluorine-containing chain ester include cf3c(=o)oc2f5, cf3c(=o)och2cf3, CF3C(=o)och2ch2cf3, CF3C(=0)0CH2C2F5, CF3C(=0)0CH2CF2CF2H, CF3C(=0)0CH (CF3)2 'CF3C(=o)och(cf3)2, etc., in which compatibility with other solvents, viscosity, oxidation resistance, etc. is good, with cf3c(= 〇)〇c2f5, CF3C( = 0) 0CH2C2F5, CF3C(= o)och2cf2cf2h, CF3C(=0)0CH2CF3, CF3C(=0)0CH(CF3)2 are particularly good. The fluorine-containing lactone can be exemplified by the formula (5): -20- 201142885
OMMCOMMC
X9X10C o (5) CX7X'X9X10C o (5) CX7X'
X5X6C (式中,X5〜xi〇爲相同或相異,皆爲_H、-F、-Cl、-CH3 或含氟甲基;但,X5〜X10之至少1個爲含氟甲基)所示之 含氟內酯。 含氟內酯除前述式(5)所示者以外,例如尙亦可舉出式 (6): [化 10] 人 (6) r fe—xJ1a xx^x1 / \ X14 X15 (式中’ A及B之任一者爲CX16X17(X16及X17爲相同或相 異,皆爲-H、-F、-Cl、-CF3、-CH3或氮原子可被_素原 子所取代而可在鏈中含有雜原子之烷基),而另一方爲氧 原子;Rfe爲含氟醚基 '含氟烷氧基或碳數2以上之含氣 烷基;X11及X12爲相同或相異,皆爲-H、-F、-Cl、 或-CH3; X13〜X15爲相同或相異,皆爲-H、-F、-C1或氫 原子可被鹵素原子所取代之在鏈中可含有雜原子之院基; -21 - 201142885 n=0或1)所示之含氟內醋等。 此等之中,由可特別發揮高介電率、高耐電壓之優異 特性之觀點,及由其他電解質鹽之溶解性、內部電阻下降 良好之觀點,並由提升作爲本發明中之電層液之特性之觀 點,以下述者爲佳。 [化 11]X5X6C (wherein, X5 to xi〇 are the same or different, and are all _H, -F, -Cl, -CH3 or a fluorine-containing methyl group; however, at least one of X5 to X10 is a fluorine-containing methyl group) Fluoride lactone is shown. In addition to those shown in the above formula (5), the fluorine-containing lactone may be, for example, a formula (6): [Chemical 10] Person (6) r fe—xJ1a xx^x1 / \ X14 X15 (wherein A And B is either CX16X17 (X16 and X17 are the same or different, and all are -H, -F, -Cl, -CF3, -CH3 or a nitrogen atom may be substituted by a _ atom and may be contained in the chain The alkyl group of the hetero atom and the other is an oxygen atom; Rfe is a fluorine-containing ether group 'fluorinated alkoxy group or a gas-containing alkyl group having a carbon number of 2 or more; X11 and X12 are the same or different, and all are -H , -F, -Cl, or -CH3; X13~X15 are the same or different, all of which are -H, -F, -C1 or a hydrogen atom which can be substituted by a halogen atom and which may contain a hetero atom in the chain. ; -21 - 201142885 n = 0 or 1) Fluorine-containing vinegar, etc. Among these, from the viewpoint of exhibiting excellent characteristics of high dielectric constant and high withstand voltage, and from the viewpoints of good solubility of other electrolyte salts and deterioration of internal resistance, it is promoted as an electric layer liquid in the present invention. The viewpoint of the characteristics is preferably as follows. [化11]
'οI'οI
OHCOHC
OHCOHC
2 H 、cI 'o — H b. c f3ch2-hc-ch2 c f3c f2-hc-ch22 H , cI 'o — H b. c f3ch2-hc-ch2 c f3c f2-hc-ch2
OHCOHC
OHC H sc. d, 2 H VC. c2 f5ch2-hc-ch2 _ 3 F F CIC 3 p c C ΗOHC H sc. d, 2 H VC. c2 f5ch2-hc-ch2 _ 3 F F CIC 3 p c C Η
Η C 〇=c /ο· F C ΗΗ C 〇=c /ο· F C Η
-c 2 H Η c 者 述 下 如 用 使 可 亦 酯 內 氟 含 他 其 -22- 201142885 [化 12]-c 2 H Η c is described as if it is used to make the ester also contain fluorine. -22- 201142885 [Chem. 12]
onNConNC
OMMCOMMC
d——c 2 2 Η HD——c 2 2 Η H
'c- 2 H'c- 2 H
•c 2 H F b-c o=c•c 2 H F b-c o=c
c-c H FC-c H F
2 H Η b——c OHnc o = c2 H Η b——c OHnc o = c
c-c 2 2 F H H b — cC-c 2 2 F H H b — c
-c. 2 H-c. 2 H
,c 2 H F H 、oIc, c 2 H F H , oIc
cIc 2 2 F H o=c 2 F bic 含氟環丁颯衍生物可例不如日本特開200Π32994號 公報中記載之含氟環丁颯衍生物,其中亦以下述者爲佳。 [化 13]cIc 2 2 F H o = c 2 F bic The fluorine-containing cyclobutyl hydrazine derivative is not limited to the fluorine-containing cyclobutyl hydrazine derivative described in JP-A No. 200 Π 32994, and the following is preferred. [Chem. 13]
F 〇v yO Ο. .〇 〇 〇F 〇v yO Ο. .〇 〇 〇
FF
FF
FF
FF
F 〇\ yCH2C2 F s V°.CHiCF,F 〇\ yCH2C2 F s V°.CHiCF,
oo
CH2C F aCHF 作爲式(1)所不之含氟環狀碳酸鹽之共溶劑而使用之非 氟系電解質鹽溶解用溶劑,可舉出非氟系環狀碳酸鹽、非 •23- 201142885 氟系鏈狀碳酸鹽、非氟系鏈狀酯、非氟系鏈狀醚、非氟系 內酯、非氟系環丁颯衍生物、其他非氟系電解質鹽溶解用 溶劑等。 非氟系環狀碳酸鹽,例如可舉出下述等。 [化 14]CH2C F aCHF The solvent for dissolving the non-fluorine-based electrolyte salt used as a co-solvent of the fluorine-containing cyclic carbonate which is not contained in the formula (1), and examples thereof include a non-fluorine-based cyclic carbonate and a non-fluorinated bicarbonate. A chain carbonate, a non-fluorine chain ester, a non-fluorine chain ether, a non-fluoro lactone, a non-fluorocyclobutanine derivative, and a solvent for dissolving other non-fluorine electrolyte salts. Examples of the non-fluorine-based cyclic carbonate include the following. [Chem. 14]
OHMC onnc ό — c H I 3 H c 2 H bIcOHMC onnc ό — c H I 3 H c 2 H bIc
2 H ό——c 2 Η b—c2 H ό——c 2 Η b-c
OHCOHC
ό——c H H b——c 式 以 如 例 鹽 酸 碳 狀 Ϊ _ 鏈 系 氟 非 [化 15]Ό——c H H b——c is as in the case of salt acid carbon Ϊ _ chain system fluorine non-chemical [Chemical 15]
Ο II (7)Ο II (7)
Ral-〇-C-〇-R :式中,Ral及Ra2爲相同或相異,皆爲碳數1〜4之烷基) 听示之鏈狀碳酸鹽爲佳。 非氟系鏈狀碳酸鹽之中,由可特別發揮高介電率、高 酎電壓之優異特性之觀點,及由其他電解質鹽之溶解性、 內部電阻下降良好之觀點,並由提升作爲本發明雙中之雙 -24- 201142885 電層電谷器之特性之觀點,以下述者等爲佳。 [化 16] Ο CH3CH2CHa~O-C-〇-CH2CH2CH3 Ο CH3CH2-O-C-O-CH2CH3 0 、II CH3-0-c-〇-ch3 、 9Η3 o ch3I II I CH3CH-0-C-0-CHCH3 o CH3CH2-〇-C-〇-CH3其他非氟系鏈狀碳酸鹽亦可使用如下述等。 [化Π] 〇II CH3CH2CH2-〇-C-〇-CH3 、 0II ch3ch2ch2-o-c-o-ch2ch3 Ηc I 0 1OHnc Io 3 I Η H CIC 3 HcRal-〇-C-〇-R: wherein Ral and Ra2 are the same or different, and each is an alkyl group having 1 to 4 carbon atoms. It is preferred to hear the chain carbonate. Among the non-fluorine-based chain carbonates, from the viewpoint of exhibiting excellent characteristics of high dielectric constant and high enthalpy voltage, and from the viewpoints of good solubility of other electrolyte salts and a decrease in internal resistance, the present invention is improved. The characteristics of the double-double--24-201142885 electric layer electric grid device are preferably the following. Ο CH3CH2CHa~OC-〇-CH2CH2CH3 Ο CH3CH2-OCO-CH2CH3 0 , II CH3-0-c-〇-ch3 , 9Η3 o ch3I II I CH3CH-0-C-0-CHCH3 o CH3CH2-〇- Other non-fluorine-based chain carbonates of C-〇-CH3 can also be used as described below. [ΠΠ] 〇II CH3CH2CH2-〇-C-〇-CH3, 0II ch3ch2ch2-o-c-o-ch2ch3 Ηc I 0 1OHnc Io 3 I Η H CIC 3 Hc
Hc 2 Hc 1 0 1o=c 1o 3. I Η H CIC 3 Hc 此等之作爲式(1)所示之含氟環狀碳酸鹽之共溶劑所使 用之電解質鹽溶解用溶劑,由耐氧化性、黏性爲良好之觀 -25- 201142885 點,以含氟電解質鹽溶解用溶劑爲佳,以含氟鏈狀碳酸鹽 、含氟鏈狀酯、含氟鏈狀醚爲更佳。特別係作爲以3.5 V 以上之高電壓使其動作時之溶劑(IIA),以式(1)所示之含 氟環狀碳酸鹽,與選自僅由含氟鏈狀碳酸鹽、含氟鏈狀酯 及含氟鏈狀醚所成群之至少1種所構成者爲佳,其中,由 耐氧化性爲良好之觀點,以含氟鏈狀醚爲佳。 特佳之含氟環狀碳酸鹽與含氟鏈狀醚之組合,特別係 由耐氧化性、電解質鹽之溶解性爲良好之觀點,爲下述之 含氟環狀碳酸鹽,與 [化 18] Ο ΟHc 2 Hc 1 0 1o=c 1o 3. I Η H CIC 3 Hc The solvent for dissolving the electrolyte salt used as the co-solvent of the fluorine-containing cyclic carbonate represented by the formula (1), which is resistant to oxidation The viscosity is good. From -25,42,885, the solvent for dissolving the fluorine-containing electrolyte salt is preferred, and the fluorine-containing chain carbonate, the fluorine-containing chain ester, and the fluorine-containing chain ether are more preferable. In particular, the solvent (IIA) which is operated at a high voltage of 3.5 V or higher, the fluorine-containing cyclic carbonate represented by the formula (1), and the fluorine-containing chain carbonate and the fluorine-containing chain are selected. It is preferable that at least one of a group of the ester and the fluorine-containing chain ether is formed, and among them, a fluorine-containing chain ether is preferred from the viewpoint of good oxidation resistance. The combination of a fluorine-containing cyclic carbonate and a fluorine-containing chain ether is particularly preferred from the viewpoints of good oxidation resistance and solubility of an electrolyte salt, and is a fluorine-containing cyclic carbonate described below. Ο Ο
〇 I 〇 〇 1 0 1 1 FHC — | ——ch2 2 喊 cf3-hc 1 CH_ 選自由 CF3CF2CH2-O-CF2CFHCF3 ' HCF2CF2CH2-O-CF2CFHCF3 、cf3cf2ch2-〇-cf2cf2h 及 hcf2cf2ch2-o-cf2cf2h 所成 群之至少1種之含氟鏈狀醚之混合物。 (IIB)電解質鹽 電解質鹽(ΠΒ)除可舉出以往公知之銨鹽、金屬鹽,尙 可舉出液體狀之鹽(離子性液體)、無機高分子型之鹽、有 機高分子型之鹽等。 銨鹽可使用以往公知者,例如可舉出螺環聯吡啶鑰鹽 、咪唑鑰鹽、四烷基4級銨鹽、N-烷基吡啶鑰鹽、N,N-二 -26- 201142885 烷基吡咯啶鑰鹽等。 螺環聯吡啶鑰鹽,例如較佳可舉出式(1 0-1): [化 19] (Ώ 1 ίτ> t 1\〇I 〇〇1 0 1 1 FHC — | ——ch2 2 Shout cf3-hc 1 CH_ Select CF3CF2CH2-O-CF2CFHCF3 ' HCF2CF2CH2-O-CF2CFHCF3 , cf3cf2ch2-〇-cf2cf2h and hcf2cf2ch2-o-cf2cf2h A mixture of at least one of the fluorine-containing chain ethers. (IIB) Electrolyte salt Electrolyte salt (ΠΒ) may, for example, be a conventionally known ammonium salt or a metal salt, and examples thereof include a liquid salt (ionic liquid), an inorganic polymer salt, and an organic polymer salt. Wait. The ammonium salt can be used by a conventionally known one, and examples thereof include a spirocyclic pyridinium salt, an imidazolium salt, a tetraalkyl 4-ammonium salt, an N-alkyl pyridyl salt, and an N,N-di-26-201142885 alkyl group. Pyrrolidine key salt and the like. The spirobipyridine salt is preferably, for example, a formula (1 0-1): [Chem. 19] (Ώ 1 ίτ> t 1\
\_/㊉\_/ (式中,Rfl及Rf2爲相同或相異,皆爲碳數1〜4之烷基; X旧陰離子;nl爲0〜5之整數;n2爲0〜5之整數)所示 之螺環聯吡啶鑰鹽、式(1 〇 - 2 ): [化 20]\_/十\_/ (wherein, Rfl and Rf2 are the same or different, all are C 1~4 alkyl; X old anion; nl is an integer of 0~5; n2 is an integer of 0~5 ) a spirobipyridine key salt, formula (1 〇-2): [Chem. 20]
X0 (式中,Rf3及Rf4爲相同或相異,皆爲碳數1〜4之烷基; X_爲陰離子;n3爲0〜5之整數;n4爲0〜5之整數)所示 之螺環聯吡啶鑰鹽,或式(1 〇 - 3 ):X0 (wherein Rf3 and Rf4 are the same or different, each is an alkyl group having 1 to 4 carbon atoms; X_ is an anion; n3 is an integer of 0 to 5; n4 is an integer of 0 to 5) Cyclopyridine salt, or formula (1 〇-3):
(10-3) -27- 201142885 (式中,Rf5及Rf6爲相同或相異,皆爲碳數1〜4之烷基; X_爲陰離子;n5爲0〜5之整數;π6爲0〜5之整數)所示 之螺環聯吡啶鑰鹽。又,由提升耐氧化性之觀點,亦以此 螺環聯吡啶鑰鹽之氫原子之一部分或全部被氟原子及/或 碳數1〜4之含氟烷基所取代者爲佳。 陰離子Χ_可爲無機陰離子亦可爲有機陰離子。無機陰 離子例如可舉出 A1C14_、BF4_、PF6_、AsF6·、TaF6·、Γ、 SbF6·等。又,有機陰離子例如可舉出CH3COCT、CF3S03· 、(CF3S02)2N·、(C2F5S02)2N·等。此等之中,由解離性 爲高,高電壓下之內部電阻爲低之觀點,以BF4_、PF6_、 (cf3so2)2n-或(c2f5so2)2n_爲佳,特別係以 bf4-、pf6-爲 更佳。 螺環聯吡啶鑰鹽之較佳具體例,例如可舉出下述等。 [化 22](10-3) -27- 201142885 (wherein Rf5 and Rf6 are the same or different, each is an alkyl group having 1 to 4 carbon atoms; X_ is an anion; n5 is an integer of 0 to 5; π6 is 0~ A spirobipyridine salt represented by an integer of 5). Further, from the viewpoint of enhancing oxidation resistance, it is preferred that one or all of the hydrogen atoms of the spirobipyridine salt be replaced by a fluorine atom and/or a fluorine-containing alkyl group having 1 to 4 carbon atoms. The anion Χ_ may be an inorganic anion or an organic anion. Examples of the inorganic anion include A1C14_, BF4_, PF6_, AsF6·, TaF6·, Γ, SbF6· and the like. Further, examples of the organic anion include CH3COCT, CF3S03·, (CF3S02)2N·, (C2F5S02)2N· and the like. Among these, from the viewpoint that the dissociation property is high and the internal resistance at high voltage is low, BF4_, PF6_, (cf3so2)2n- or (c2f5so2)2n_ is preferable, especially bf4-, pf6- Better. Preferable specific examples of the spirobipyridyl key salt include the following. [化22]
-28- 201142885 此螺環聯吡啶鑰鹽在對溶劑之溶解性、耐氧化性、離 子傳導性之面上優異。 咪唑鑰鹽較佳可舉出例如式(1 1): [化 23] /R81 (11) \N 〆 χθ-28- 201142885 This spirobipyridine salt is excellent in solubility in a solvent, oxidation resistance, and ion conductivity. The imidazole key salt is preferably, for example, a formula (1 1): [Chem. 23] / R81 (11) \N 〆 χ θ
(式中,Rgi及Rg2爲相同或相異,皆爲碳數1〜6之烷基 ;乂_爲陰離子)所示之咪唑鑰鹽。又,由提升耐氧化性之 觀點,亦以此咪唑鑰鹽之氫原子之一部分或全部被氟原子 及/或碳數1〜4之含氟烷基所取代者爲佳。 陰離子X_之較佳具體例係與螺環聯吡啶鑰鹽相同。 .咪唑錙鹽之較佳具體例,例如可舉出式(1 2): [化 24](wherein, Rgi and Rg2 are the same or different, each are an alkyl group having 1 to 6 carbon atoms; and 乂 is an anion). Further, from the viewpoint of enhancing oxidation resistance, it is preferred that one or all of the hydrogen atoms of the imidazole salt are replaced by a fluorine atom and/or a fluorine-containing alkyl group having 1 to 4 carbon atoms. A preferred specific example of the anion X_ is the same as the spirobipyridine salt. Preferred examples of the imidazolium salt include, for example, the formula (1 2):
HSC Χθ (12) 所示之乙基甲基咪唑鑰鹽等》 此咪唑鑰鹽黏性爲低,且對溶劑之溶解性爲優良。 四烷基4級銨鹽較佳可舉出例如式(1 3 ): -29 - 201142885 [化 25]HSC Χ θ (12) Ethylmethylimidazole key salt, etc. This imidazole key salt has low viscosity and is excellent in solubility in a solvent. The tetraalkyl 4-based ammonium salt is preferably, for example, a formula (1 3 ): -29 - 201142885 [Chem. 25]
Rh 1Rh 1
I ® AI ® A
Rh2_N_Rh4 (13)Rh2_N_Rh4 (13)
II
Rh3 (式中,Rhl、Rh2 ' Rh3及Rh4爲相同或相異,皆爲可含有 碳數1〜6之醚結合之烷基;X·爲陰離子)所示之四烷基4 級銨鹽。又,由提升耐氧化性之觀點,亦以此四烷基4級 銨鹽之氫原子之一部分或全部被氟原子及/或碳數1〜4之 含氟烷基所取代者爲佳。 具體例可舉出 式(13-1): [化 26] (Rhl) , (Rh2) ,ΝΘ Χθ (13-1〉 (式中、Rhl、Rh2及厂與式(13)相同:χ及y爲相同或相異 ,〇〜4之整數,且x+y=4)所示之四烷基4級銨鹽、 式(13-2): [化 27]Rh3 (wherein, Rhl, Rh2 'Rh and Rh4 are the same or different, and each is an alkyl group which may contain an ether having a carbon number of 1 to 6; X. is an anion). Further, from the viewpoint of enhancing oxidation resistance, it is preferred that one or all of the hydrogen atoms of the tetraalkyl 4-membered ammonium salt be replaced by a fluorine atom and/or a fluorine-containing alkyl group having 1 to 4 carbon atoms. Specific examples include the formula (13-1): [Chem. 26] (Rhl), (Rh2), ΝΘ Χ θ (13-1> (wherein, Rhl, Rh2, and the plant are the same as the formula (13): χ and y Is the same or different, 整数~4 integer, and x+y=4) is a tetraalkyl 4- toluene salt, formula (13-2): [Chem. 27]
h Rh R
φ N HRφ N HR
Θ X οΘ X ο
h R 2 - 3 (式中,Rh5爲碳數1〜.6之烷基·,Rh6爲碳數丨〜6之2價 烴基;Rh7爲碳數之烷基:2爲1或2; X·爲陰離子) -30- 201142885 所示之含烷基醚基之三烷基銨鹽等<•藉由導入烷基醚基而 可謨求黏性降低。 陰離子X·之較佳具體例係與螺環聯吡啶鏺鹽相同。 四烷基4級銨鹽之適宜具體例,例如可舉出Et4NBF4 ' Et4NC104 、 Et4NPF6 、 Et4NAsF6 、 Et4NSbF6 、 Et4NCF3S03、Et4N(CF3S02)2N、Et4NC4F9S03、Et3MeBF4 、Et3MeC104 、 Et3MePF6 、 Et3MeAsF6 、 Et3MeSbF6 、 Et3MeCF3S03 ' E13 M e (C F 3 S O 2) 2 N、E13 M e C 4 F 9 S O 3 等,特 別係以 Et4NBF4、Et4NPF6、Et4NSbF6、Et4NAsF6(Me 爲甲 基、Et爲乙基)等爲佳。 N-烷基吡啶鑰鹽較佳可舉出例如式(14): [化 28]h R 2 - 3 (wherein Rh 5 is an alkyl group having a carbon number of 1 to 6.), Rh 6 is a divalent hydrocarbon group having a carbon number of 丨 to 6; and Rh 7 is an alkyl group having a carbon number: 2 is 1 or 2; The alkyl ether group-containing trialkylammonium salt represented by anion) -30- 201142885 <• can be reduced in viscosity by introducing an alkyl ether group. A preferred specific example of the anion X· is the same as the spirobipyridinium salt. Specific examples of the tetraalkyl 4-grade ammonium salt include Et4NBF4 ' Et4NC104 , Et4NPF6 , Et4NAsF6 , Et4NSbF6 , Et4NCF3S03 , Et4N(CF3S02) 2N , Et4NC4F9S03 , Et3MeBF4 , Et3MeC104 , Et3MePF6 , Et3MeAsF6 , Et3MeSbF6 , Et3MeCF3S03 ' E13 M e (CF 3 SO 2) 2 N, E13 M e C 4 F 9 SO 3 , etc., particularly preferably Et4NBF4, Et4NPF6, Et4NSbF6, Et4NAsF6 (Me is methyl, Et is ethyl) and the like. The N-alkylpyridyl key salt is preferably, for example, a formula (14):
(1 4) (式中’ Rn爲氫原子或碳數1〜6之烷基;X·爲陰離子)所 不之N -院基卩比陡鑰鹽。又,由提升耐氧化性之觀點,亦 以此N-烷基吡啶鎗鹽之氫原子之一部分或全部被氟原子 及/或碳數1〜4之含氟烷基所取代者爲佳。 陰離子X_之較佳具體例係與螺環聯吡啶鑰鹽相同。 較佳具體例,例如可舉出如下述等。 -31 - 201142885 [化 29](1 4) (wherein Rn is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; X is an anion). Further, from the viewpoint of enhancing oxidation resistance, it is preferred that one or all of the hydrogen atoms of the N-alkylpyridine salt are replaced by a fluorine atom and/or a fluorine-containing alkyl group having 1 to 4 carbon atoms. A preferred specific example of the anion X_ is the same as the spirobipyridine salt. Preferred examples thereof include, for example, the following. -31 - 201142885 [Chem. 29]
bf4Qbf4Q
pf6®Pf6®
pf60 F θ 此N-烷基吡啶鑰鹽黏性爲低,且對溶劑之溶解性優 良。 N,N-二烷基吡咯啶鑰鹽較佳可舉出例如式(15): [化 30] RJ 2 RJ »Pf60 F θ This N-alkylpyridinium salt has low viscosity and excellent solubility in a solvent. The N,N-dialkylpyrrolidine key salt is preferably, for example, a formula (15): [Chem. 30] RJ 2 RJ »
(式中,Rjl及Rj2爲相同或相異,皆爲碳數1〜6之烷基; -32- 201142885 X-爲陰離子)所示之N,N-二烷基吡咯啶鑰鹽。又’由提升 耐氧化性之觀點,亦以此N,N-二烷基吡咯啶鑰鹽之氫原子 之一部或全部被氟原子及/或碳數1〜4之含氟烷基所取代 者爲佳。 陰離子X_之較佳具體例係與螺環聯吡啶鎗鹽相同。 較佳之具體例,例如可舉出如下述者。 [化 31] CH3 ^ch3(wherein, Rjl and Rj2 are the same or different, each are an alkyl group having 1 to 6 carbon atoms; -32- 201142885 X- is an anion) represented by an N,N-dialkylpyrrolidine key salt. Further, from the viewpoint of improving oxidation resistance, one or all of the hydrogen atoms of the N,N-dialkylpyrrolidine salt are replaced by fluorine atoms and/or fluorine-containing alkyl groups having 1 to 4 carbon atoms. It is better. A preferred specific example of the anion X_ is the same as the spirobipyridine gun salt. Preferred examples of the preferred embodiment include the following. [化31] CH3 ^ch3
bf4Qbf4Q
pf6°Pf6°
33- 20114288533- 201142885
此N,N-二烷基吡咯啶鑰鹽黏性爲低,且對溶劑之溶解· 性優良。 此等銨鹽之中,螺環聯吡啶銷鹽及咪唑鐡鹽,由對溶 劑之溶解性、耐氧化性、離子傳導性之觀點而爲佳,並以 下述者爲佳。 -34- 201142885 [化 33]The N,N-dialkylpyrrolidine salt has low viscosity and excellent solubility in a solvent. Among these ammonium salts, the spirobipyridinium salt and the imidazolium salt are preferably from the viewpoints of solubility in the solvent, oxidation resistance, and ion conductivity, and are preferably the following. -34- 201142885 [Chem. 33]
(式中 ’ X·爲 BF4、PF6、(CF3S〇2)2N_ 或(c2f5S〇2)2N—,特 別以PF6·爲佳),或 [化 34](where X ' is BF4, PF6, (CF3S〇2) 2N_ or (c2f5S〇2) 2N-, especially PF6· is preferred), or [34]
(式中,X-爲 BF4-、PF6-、(CF3S02)2N·或(C2F5S02)2N·,特 別以BFr、PF6_爲佳)。 又,電解質鹽可倂用鋰鹽。鋰鹽例如以LiPF6、LiBF4 、LiAsF6、LiSbF6、LiN(S02C2H5)2 爲佳。 更且,爲了使靜電容量提升,亦可使用鎂鹽。鎂鹽係 例如以 Mg(C104)2、Mg(OOC2H5)2 等爲佳。 特別係將前述式(1)之含氟環狀碳酸鹽作爲氟系溶劑 (IIA)使用時,以由 BF4-、PF6-、N(02SC2F5)2 或 N(02SCF3)之 陰離子所構成之環狀4級鑰鹽爲佳。 電解質鹽(IIB)之配合量係依據所要求之電流密度、用 途、電解質鹽之種類等而異,相對於含氟環狀碳酸鹽(倂 用其他電解質鹽溶解用溶劑時爲彼等之合計量)100質量份 -35- 201142885 ’爲〇 · 1質量份以上’ 1質量份以上爲更佳,5質量份以 上爲特佳’並爲200質量份以下,1〇〇質量份以下爲更佳 ,50質量份以下爲特佳。 本發明所用之電解液係藉由使電解質鹽(ΙΙΒ)溶解於氟 系溶劑(ΙΙΑ)而調製。 又,本發明中’電解液亦可溶解於本發明之電解液所 使用之溶劑中或與膨潤之高分子材料組合而成爲凝膠狀( 經可塑化)之凝膠電解液。 該高分子材料,可舉出以往公知之聚環氧乙烷或聚環 氧丙烷,彼等之改質物(日本特開平8-222270號公報、日 本特開2002-10 04 05號公報);聚丙烯酸酯系聚合物、聚丙 烯腈、或聚偏二氟乙烯、二氟乙烯-六氟丙烯共聚物等之 氟樹脂(日本特表平4-506726號公報、日本特表平8-5074〇7號公報、日本特開平1 0 — 294 1 3 1號公報);該等氟 樹脂與烴系樹脂之複合物(日本特開平1 1 -3 5 765號公報、 曰本特開平1 1 -86630號公報)等。特別係以將聚偏二氟乙 嫌、二氟乙烯-六氟丙烯共聚物作爲凝膠電解質用高分子 材料使用爲理想。 其他亦可使用日本特願2004-301 934號說明書中記載 之離子傳導性化合物》 本發明所使用之電解液可因應需要配合其他添加劑。 其他添加劑可舉出例如金屬氧化物、玻璃等。. 此般電解液由於不僅可維持低溫特性,亦可同時使難 燃性、電解質鹽之溶解性及與烴系溶劑之相溶性提升,並 且可得到在3.5V以上之耐電壓下安定之特性,而可優異 •36- 201142885 作爲雙電層電容器之電解液。 雙電層電容器一般已知有捲繞電池型雙電層電容器、 積層型雙電層電容器、硬幣型雙電層電容器等,本發明之 雙電層電容器亦可成爲此等之形式。 例如捲繞電池型雙電層電容器係將由集電體與電極層 之積層體(電極)所構成之正極及負極經由間隔器隔開而捲 繞製作成捲繞元件,並將此捲繞素子放入鋁製等之外殼, 在注滿電解液,較佳爲非水系電解液後,藉由以橡膠製之 封口物封閉進行密封而組成。 本發明之電極因配合有丙烯酸系化合物(ID),而具有 充分之機械特性,特別係耐彎曲性,故可容易且安定地製 作捲繞元件,又其耐久性亦爲優異。 本發明中作爲間隔器可使用以往公知之材料與構成者 。例如,可舉出聚乙烯多孔質膜、聚丙烯纖維或玻璃繊維 、纖維素纖維之不織布等。 又’藉由公知之方法,亦可作成將經由電解液與間隔 器而隔開之薄片狀之正極及負極予以積層之積層型雙電層 電容器’或由藉墊片固定將經由電解液與間隔器隔開之正 極及負極構成爲硬幣型之硬幣型雙電層電容器。 [實施例] 以下,基於實施例及比較例說明本發明,但並本發明 並非係侷限於該等例者。 實施例1(電極之製作) -37- 201142885 (電極用漿體之調製) 將經水蒸氣活化之難石墨化活性碳粒子(KURARAY CHEMICAL(股)製之 YP50F、比表面積:1600m2/g、平均 粒徑6μιη) 100重量份、作爲導電助劑之乙炔黑(電氣化學 工業(股)製之Denka Black)3重量份、科琴黑(LION(股)製 之 Carbon ECP600JD)16重量份、彈性體黏合劑(曰本 ΖΕΟΝ(股)製之ΑΖ-900 1 )6重量份、增黏材(東亞合成(股) 製之Α10Η)3重量份予以混合而調製成電極用漿體。 (電極之製作) 準備作爲集電體之蝕刻式鋁片(etched aluminium)(曰 本蓄電器工業(股)製之20CB、厚度約20μιη),對此集電體 之兩面使用塗裝裝置塗布導電塗料(日本石墨工業(股)製之 Varniphite Τ602),而形成導電層(厚度:2μηι)。 其次,使用塗裝裝置將前述所調製之電極用漿體塗布 於集電體之兩面上所形成之導電層上,形成電極層(厚度 :ΙΙΟμιη),而製作成本發明之電極。 關於此電極,藉以下之要件調査電極密度及耐彎曲性 時,電極密度爲0.41 g/cm3,耐彎曲性之評價爲〇。 (1)電極密度 預先測量裁減至既定之尺寸之塗布有導電層之蝕刻式 鋁片(基材)之重量或外形尺寸,並於其上部塗布電極層。 將自塗布後以140°C使其乾燥1小時之重量減去基材之重 量分者作爲電極重量,又,自塗布後之外形體積減去基材 -38- 201142885 之外形體積,而作爲電極之外形尺寸。依據上述所算出之 電極之重量與外形寸法,算出電極密度。 (2)塗膜彎曲試驗 依據JIS K54 00,使用彎曲試驗機(安田精機製作所( 股)製之塗膜彎曲試驗機),以 Φ2之條件進行測定。評價 係以以下之基準進行。 〇:目視上,完全無發現到破裂。 X :目視上,發現到裂紋。 實施例2(電容器之製作) 將實施例1中製作之電極裁切爲31111111寬。將此電極 與間隔器(日本高度紙工業(股)製之TF45 -3 0、寬34cm) — 同地使用EDLC用捲繞機進行捲繞’而製作成直徑16mm 之圓筒捲繞體。此時,對電極與電極引出用之導線進行塡 隙連接。 其次,使製成之圓筒捲繞體、圓筒鋁殼 '橡膠墊圈真 空乾燥後,在乾燥室中’將圓筒捲繞體插入圓筒鋁殼’其 後,注入以下所示之電解液,藉由經由橡膠墊圈進行密封 ,而製作成捲繞電池型之電容器(φ 1 8mmx40mm)。 (電解液之調製) 將環丁颯與hcf2cf2ch2ocf2cf2h與二甲基碳酸鹽以 體積比65/1 5/20進行混合而調製成電解質鹽溶解用溶劑。 對此電解質鹽溶解用溶劑以能成爲K2莫耳/公升濃度添加 -39- 201142885 四氟化硼酸螺聯吡啶鑰鹽,而成均勻之溶液,並將此溶液 作爲電解液使用。 關於製成之電容器,藉以下之方法調査其初期特性( 靜電容量(F)、內部電阻(ηιΩ))、低溫特性(靜電容量保持率 (%)、電阻增加率(倍))及耐電壓(以3V與3.1 V進行長期信 賴性評價)。其結果如表1所示。 (3)初期特性 對電容器之捲繞電池連接電子電源後,對捲繞電池以 定電流進行充電,同時使充電電壓上升至規定電壓爲止》 充電電壓到達規定電壓後維持1 〇分鐘定電壓狀態,並在 確認充電電流充分下降且成爲飽和狀態後,開始定電流放 電,以每0.1秒之間隔計測電池電壓。電容器之靜電容量 (F)及內部電阻(ιηΩ)係依據社團法人電子情報技術產業協 會(JEITA)之RC23 77之計測方法進行計測。 (JEITA之RC2377下之計測條件)(wherein X- is BF4-, PF6-, (CF3S02)2N· or (C2F5S02)2N·, especially BFr and PF6_ are preferred). Further, the electrolyte salt may be a lithium salt. The lithium salt is preferably LiPF6, LiBF4, LiAsF6, LiSbF6 or LiN(S02C2H5)2, for example. Further, in order to increase the electrostatic capacity, a magnesium salt can also be used. The magnesium salt is preferably Mg (C104) 2, Mg (OOC2H5) 2 or the like, for example. In particular, when the fluorine-containing cyclic carbonate of the above formula (1) is used as the fluorine-based solvent (IIA), the ring is composed of an anion of BF4-, PF6-, N(02SC2F5)2 or N(02SCF3). Level 4 key salt is preferred. The amount of the electrolyte salt (IIB) varies depending on the required current density, the use, the type of the electrolyte salt, and the like, and is equivalent to the fluorine-containing cyclic carbonate (the total amount of the solvent used for dissolving other electrolyte salts) 100 parts by mass -35 - 201142885 'It is 1 part by mass or more' 1 part by mass or more is more preferable, 5 parts by mass or more is particularly good' and 200 parts by mass or less, and 1 part by mass or less is more preferable. 50 parts by mass or less is particularly preferred. The electrolytic solution used in the present invention is prepared by dissolving an electrolyte salt (ΙΙΒ) in a fluorine-based solvent. Further, in the present invention, the electrolytic solution may be dissolved in the solvent used in the electrolytic solution of the present invention or combined with the swollen polymer material to form a gel-like (plasticized) gel electrolyte. The polymer material may be a conventionally known polyethylene oxide or polypropylene oxide, and the modified materials thereof (Japanese Patent Laid-Open Publication No. Hei 8-222270, No. 2002-10 04 05); A fluororesin such as an acrylate polymer, a polyacrylonitrile, or a polyvinylidene fluoride or a difluoroethylene-hexafluoropropylene copolymer (Japanese Patent Publication No. 4-506726, Japanese Patent Application No. 8-5074〇7) Japanese Unexamined Patent Publication No. Hei No. Hei No. Hei No. Hei 1 1 - No. Bulletin) and so on. In particular, it is preferred to use a polyvinylidene fluoride-containing or a difluoroethylene-hexafluoropropylene copolymer as a polymer material for a gel electrolyte. Others may use the ion-conducting compound described in the specification of Japanese Patent Application No. 2004-301 934. The electrolytic solution used in the present invention may be blended with other additives as needed. Other additives include, for example, metal oxides, glass, and the like. In this way, the electrolyte can not only maintain the low-temperature characteristics, but also improve the flame retardancy, the solubility of the electrolyte salt, and the compatibility with the hydrocarbon solvent, and can obtain the stability characteristics under a withstand voltage of 3.5 V or more. It is excellent in 36-201142885 as an electrolyte for electric double layer capacitors. An electric double layer capacitor is generally known as a wound battery type electric double layer capacitor, a laminated electric double layer capacitor, a coin type electric double layer capacitor, etc., and the electric double layer capacitor of the present invention can also be in the form of these. For example, in a wound battery type electric double layer capacitor, a positive electrode and a negative electrode including a laminate (electrode) of a current collector and an electrode layer are separated by a spacer and wound into a wound element, and the wound element is placed. The outer casing of aluminum or the like is filled with an electrolyte, preferably a non-aqueous electrolyte, and then sealed by sealing with a rubber seal. Since the electrode of the present invention has sufficient mechanical properties, particularly bending resistance, by incorporating an acrylic compound (ID), it can be easily and stably produced as a wound element, and its durability is also excellent. In the present invention, conventionally known materials and constituents can be used as the spacer. For example, a polyethylene porous film, a polypropylene fiber or a glass fiber, a nonwoven fabric of cellulose fibers, or the like can be given. Further, by a known method, a laminated electric double layer capacitor in which a sheet-like positive electrode and a negative electrode which are separated by an electrolyte and a spacer are laminated may be formed or fixed by a gasket to be passed through an electrolyte and an interval. The positive electrode and the negative electrode separated by the separator are formed into a coin type coin-type electric double layer capacitor. [Examples] Hereinafter, the present invention will be described based on examples and comparative examples, but the present invention is not limited to the examples. Example 1 (Production of Electrode) -37- 201142885 (Preparation of slurry for electrode) Non-graphitizable activated carbon particles activated by steam (YP50F, KURARAY CHEMICAL, specific surface area: 1600 m2/g, average 100 parts by weight of a particle size of 6 parts by weight, acetylene black (Denka Black, manufactured by Electric Chemical Industry Co., Ltd.) as a conductive auxiliary agent, 3 parts by weight of Konica Green (Carbon ECP600JD manufactured by LION Co., Ltd.), and an elastomer 6 parts by weight of a binder (manufactured by Essence Co., Ltd.) and 6 parts by weight of a tackifier (manufactured by Toago Corporation Co., Ltd.) were mixed to prepare a slurry for an electrode. (Production of Electrode) An etched aluminum (20 CB, thickness: about 20 μm) manufactured as a current collector was prepared, and a conductive coating was applied to both sides of the current collector using a coating device. (Varniphite Τ 602, manufactured by Japan Graphite Industries Co., Ltd.), and a conductive layer (thickness: 2 μηι) was formed. Next, the above-mentioned prepared electrode slurry was applied onto the conductive layer formed on both faces of the current collector by using a coating device to form an electrode layer (thickness: ΙΙΟμηη), thereby producing an electrode of the invention. With respect to this electrode, when the electrode density and the bending resistance were investigated by the following requirements, the electrode density was 0.41 g/cm3, and the bending resistance was evaluated as 〇. (1) Electrode density The weight or outer dimension of an etched aluminum sheet (substrate) coated with a conductive layer cut to a predetermined size was measured in advance, and an electrode layer was coated on the upper portion thereof. The weight of the substrate after drying from 140 ° C for 1 hour minus the weight of the substrate is taken as the weight of the electrode, and the volume outside the coating is subtracted from the volume of the substrate -38-201142885, and the electrode is used as an electrode. Outer size. The electrode density was calculated based on the weight and shape of the electrode calculated above. (2) Coating film bending test According to JIS K54 00, a bending tester (film bending tester manufactured by Yasuda Seiki Seisakusho Co., Ltd.) was used, and measurement was performed under the condition of Φ2. The evaluation was carried out on the basis of the following criteria. 〇: Visually, no cracks were found at all. X: Visually, cracks were found. Example 2 (Production of Capacitor) The electrode fabricated in Example 1 was cut to a width of 31111111. This electrode was wound with a separator (TF45-300, width 34 cm, manufactured by Nippon Paper Industries Co., Ltd.) in the same manner as in the EDLC, and a cylindrical wound body having a diameter of 16 mm was produced. At this time, the counter electrode is gap-connected to the lead wire for electrode extraction. Next, the cylindrical winding body and the cylindrical aluminum shell 'rubber gasket are vacuum-dried, and then the cylindrical winding body is inserted into the cylindrical aluminum shell in the drying chamber, and then the electrolyte shown below is injected. A capacitor of a wound battery type (φ 18 mm x 40 mm) was produced by sealing with a rubber gasket. (Preparation of Electrolyte) The cyclobutanol and hcf2cf2ch2ocf2cf2h and dimethyl carbonate were mixed at a volume ratio of 65/1 5/20 to prepare a solvent for dissolving the electrolyte salt. The solvent for dissolving the electrolyte salt was added to a concentration of K2 mol/liter to add a -39-201142885 tetrafluoroborate spiropyridine salt to form a homogeneous solution, and this solution was used as an electrolyte. For the fabricated capacitor, investigate the initial characteristics (electrostatic capacity (F), internal resistance (ηιΩ)), low-temperature characteristics (electrostatic capacity retention (%), resistance increase rate (time)), and withstand voltage (by the following methods). Long-term reliability evaluation with 3V and 3.1 V). The results are shown in Table 1. (3) Initial characteristics After the electronic battery is connected to the wound battery of the capacitor, the winding battery is charged at a constant current and the charging voltage is raised to a predetermined voltage. The charging voltage reaches a predetermined voltage and is maintained at a constant voltage of 1 〇 minutes. After confirming that the charging current has sufficiently decreased and becomes saturated, the constant current discharge is started, and the battery voltage is measured every 0.1 second. The electrostatic capacity (F) and internal resistance (ιηΩ) of the capacitor are measured in accordance with the measurement method of RC23 77 of the JEITA. (Measurement conditions under JEITA's RC2377)
電源電壓:3.0及3.IV 放電電流:500mA(製成之捲繞電池之實測靜電容量爲 50F) (4)低溫特性(-10°C) 在溫度-1 (TC之恆溫槽中放入電容器,測定各自之溫度 下之靜電容量及內部電阻値,依據以下之計算式算出靜電 容量保持率(%)及內部電阻增加率(倍)。 -40- 201142885 靜電容量保持率(%) = (-1 〇°C之靜電容量/25°C之靜電容量)χ 1 00 內部電阻增加率(倍)=(_10°C之內部電阻/25°C之內部電阻) 靜電容量保持率爲7 0%以上,且,內部電阻增加率爲 4倍以內者,即爲低溫特性特別優異者。 (5)耐電壓(長期信賴性試驗) 將捲繞電池型電容器放入溫度7 0 °C之恆溫槽中,施加 1 000小時之電壓3.0V、3.1 V,測定靜電容量與內部電阻 。測定時間爲初期(〇小時)、1 5 7小時、3 3 7小時、5 00小 時及1 000小時。由所得之測定値,依據以下之計算式算 出靜電容量保持率(%)及內部電阻上昇率(%)。其結果如表 1所示。 靜電容量保持率(%) = (各小時下之靜電容量/評價開始前(初期)之靜電容量)χΐ〇〇 內部電阻上昇率(%)=(各小時下之內部電阻/評價開始前(初期)之內部電阻)χ1〇〇 尙,500小時後之靜電容量保持率爲70%以上,且, 內部電阻上昇率爲400%以下者,即爲高溫(70°C)下之負荷 特性優良者,且常溫下之使用中之循環特性或效率性能亦 爲優良,爲具有長期信賴性者。 實施例3 作爲電解液,除了將環丁颯與hcf2cf2ch2ocf2cf2h -41 - 201142885 與二甲基碳酸鹽以體積比65/ 1 5/20進行混合而調製成電解 質鹽溶解用溶劑,對此電解質鹽溶解用溶劑以能成爲1.2 莫耳/公升濃度添加三乙基甲基銨(tema)bf4,而成均勻溶 液作爲電解液使用以外,其他與實施例2同樣地進行,製 作成捲繞電池型電容器。 對於所得之電容器,與實施例2同樣地進行,測定其 初期特性、低溫特性及耐電壓。其結果如表1所示。 實施例4 除了將環丁颯與HCF2CF2CH2OCF2CF2H以體積比75/25 進行混合而調製成電解質鹽溶解用溶劑,將對此電解質鹽 溶解用溶劑以能成爲1.2莫耳/公升濃度添加4氟化硼酸螺 聯吡啶鑰鹽而成之均勻溶液作爲電解液使用以外,其他與 實施例2同樣地進行,製成捲繞電池型電容器。 對於所得之電容器,與實施例2同樣地進行,測定其 初期特性、低溫特性及耐電壓。其結果如表1所示。 實施例5 將經水蒸氣活化之難石墨化活性碳粒子(KURARAY CHEMICAL(股)製之YP50FH、比表面積:1 600m2/g、平均 粒徑6μπι)100重量份、作爲導電助劑之乙炔黑(電氣化學 工業(股)製之Denka Black)3重量份、科琴黑(LION(股)製 之 Carbon ECP600JD)16重量份、彈性體黏合劑(日本 ΖΕΟΝ(股)製之ΑΖ-9001)6重量份、增黏材(東亞合成(股) 製之Α10Η)3重量份予以混合製成電極用漿體。 •42- 201142885 除使用此電極用漿體以外,其他與實施例1同樣地進 行製作成電極,調査電極密度及耐彎曲性時,電極密度爲 0.35g/cm3,耐彎曲性之評價爲〇》 除使用此電極以外,其他與實施例2同樣地進行,製 作成捲繞電池型電容器。 對於所得之電容器,與實施例2同樣地進行,測定其 初期特性、低溫特性及耐電壓。其結果如表1所示。 實施例6 將經水蒸氣活化之難石墨化活性碳粒子(KURARAY CHEMICAL(股)製之 YP80F、比表面積:2000m2/g、平均 粒徑6μηι) 100重量份、作爲導電助劑之乙炔黑(電氣化學 工業(股)製之Denka Black)3重量份、科琴黑(LION(股)製 之 Carbon ECP600JD)16重量份、彈性體黏合劑(日本 ΖΕΟΝ(股)製之AZ-900 1 )6重量份、增黏材(東亞合成(股) 製之A10H)3重量份予以混合調製成電極用漿體。 除使用此電極用漿體以外,其他與實施例1同樣地進 行而製作成電極,調査電極密度及耐彎曲性時,電極密度 爲0.35g/cm3,耐彎曲性之評價爲〇。 除使用此電極以外,其他與實施例2同樣地進行,製 作成捲繞電池型電容器。 對於所得之電容器,與實施例2同樣地進行,測.定其 初期特性、低溫特性及耐電壓。其結果如表1所示。 實施例7 -43- 201142885 將經水蒸氣活化之難石墨化活性碳粒子(KURARAY CHEMICAL(股)製之RP-20、比表面積:1 800m2/g、平均 粒徑8μηι)100重量份、作爲導電助劑之乙炔黑(電氣化學 工業(股)製之Denka Black)3重量份、科琴黑(LION(股)製 之 Carbon ECP600JD)16重量份、彈性體黏合劑(日本 ΖΕΟΝ(股)製之 AZ-900 1 )6重Μ份、增黏材(東亞合成(股) 製之Α10Η)3重量份予以混合而製成電極用漿體。 除使用此電極用漿體以外,其他與實施例1同樣地進 行而製作成電極,調查電極密度及耐彎曲性時,電極密度 爲0.4 1g/cm3,耐彎曲性之評價爲〇。 除使用此電極以外,其他與實施例2同樣地進行,製 作成捲繞電池型電容器。 對於所得之電容器,與實施例2同樣地進行,測定其 初期特性、低溫特性及耐電壓。其結果如表1所示。 比較例1 將經鹼活化之易石墨化活性碳粒子(KURARAY CHEMICAL (股)製之NK261、比表面積:2300m2/g、平均粒徑6μιη )1〇〇重量份、作爲導電助劑之乙炔黑(電氣化學工業(股) 製之 Denka Black)3重量份、科琴黑(LION(股)製之 Carbon ECP600JD)16重量份、彈性體黏合劑(日本ZEON( 股)製之 AZ-9001 )6重量份、增黏材(東亞合成(股)製之 A 10H) 3重量份予以混合而調製成電極用漿體。 除使用此電極用漿體以外,其他與實施例1同樣地進 行製作成電極,調査電極密度及耐彎曲性時,電極密度爲 -44 - 201142885 0.40g/cm3,耐彎曲性之評價爲〇。 除使用此電極以外,其他與實施例2同樣地 作成捲繞電池型電容器。 對所得之電容器,與實施例2同樣地進行, 期特性、低溫特性及耐電壓。其結果如表1所示 [表1] 進行,製 測定其初 -45- 201142885Power supply voltage: 3.0 and 3.IV Discharge current: 500 mA (measured electrostatic capacity of the fabricated wound battery is 50 F) (4) Low temperature characteristics (-10 ° C) Place a capacitor in the temperature -1 (TC thermostat bath) The electrostatic capacity and the internal resistance 値 at the respective temperatures were measured, and the electrostatic capacity retention ratio (%) and the internal resistance increase rate (time) were calculated according to the following calculation formula: -40- 201142885 Electrostatic capacity retention ratio (%) = (- 1 静电 ° C electrostatic capacity / 25 ° C electrostatic capacity) χ 1 00 internal resistance increase rate (time) = (_10 ° C internal resistance / 25 ° C internal resistance) electrostatic capacity retention rate of 70% or more (4) Withstand voltage (long-term reliability test) The wound battery type capacitor is placed in a thermostat bath at a temperature of 70 °C. The electrostatic capacity and internal resistance were measured by applying a voltage of 3.0 V and 3.1 V for 1 000 hours. The measurement time was initial (〇 hour), 157 hours, 327 hours, 500 hours, and 1,000 hours.値, calculate the electrostatic capacity retention rate (%) and within the following calculation formula The rate of increase in resistance (%). The results are shown in Table 1. Electrostatic capacity retention ratio (%) = (electrostatic capacity at each hour / electrostatic capacity before evaluation (initial)) χΐ〇〇 internal resistance increase rate (%) ) = (internal resistance at each hour / internal resistance before the start of evaluation (initial)) χ 1 〇〇尙, the electrostatic capacity retention rate after 500 hours is 70% or more, and the internal resistance increase rate is 400% or less. That is, it is excellent in load characteristics at high temperature (70 ° C), and is excellent in cycle characteristics or efficiency performance in use at normal temperature, and has long-term reliability. Example 3 As an electrolytic solution, except for ring oxime And hcf2cf2ch2ocf2cf2h -41 - 201142885 is mixed with dimethyl carbonate in a volume ratio of 65/1 5/20 to prepare a solvent for dissolving an electrolyte salt, and the solvent for dissolving the electrolyte salt is added to a concentration of 1.2 m/liter. In the same manner as in Example 2, a battery-type capacitor was produced in the same manner as in Example 2 except that ethyl ether was used as the electrolyte solution. The obtained capacitor was produced in the same manner as in Example 2. Determination The initial characteristics, the low-temperature characteristics, and the withstand voltage were as follows. The results are shown in Table 1. Example 4 A solvent for dissolving an electrolyte salt was prepared by mixing cyclobutane with HCF2CF2CH2OCF2CF2H at a volume ratio of 75/25. A solvent for dissolving was used in the same manner as in Example 2 except that a homogeneous solution obtained by adding a tetrafluoroborate serotonate salt to a concentration of 1.2 mol/liter was used as the electrolytic solution, thereby producing a wound battery type capacitor. The obtained capacitor was measured in the same manner as in Example 2, and its initial characteristics, low-temperature characteristics, and withstand voltage were measured. The results are shown in Table 1. Example 5 100 parts by weight of water-steam-activated non-graphitizable activated carbon particles (YP50FH, specific surface area: 1 600 m 2 /g, average particle diameter: 6 μm) manufactured by Kuraray Chemical Co., Ltd., and acetylene black as a conductive auxiliary agent ( 3 parts by weight of Denka Black manufactured by Electrochemical Industry Co., Ltd., 16 parts by weight of Ketchen Black (Carbon ECP600JD manufactured by LION Co., Ltd.), and an elastomer adhesive (ΑΖ-9001, manufactured by Nippon Co., Ltd.) 6 weight 3 parts by weight of a tackifying material (manufactured by East Asia Synthetic Co., Ltd.) was mixed to prepare a slurry for an electrode. 42-201142885 An electrode was produced in the same manner as in Example 1 except that the slurry for the electrode was used. When the electrode density and the bending resistance were examined, the electrode density was 0.35 g/cm3, and the bending resistance was evaluated as "〇". A wound battery type capacitor was produced in the same manner as in Example 2 except that this electrode was used. The obtained capacitor was measured in the same manner as in Example 2, and its initial characteristics, low-temperature characteristics, and withstand voltage were measured. The results are shown in Table 1. Example 6 100 parts by weight of non-graphitizable activated carbon particles (Kuraray Chemical Co., Ltd. YP80F, specific surface area: 2000 m 2 /g, average particle size 6 μηι) activated by steam, acetylene black as a conductive auxiliary agent (electrical 3 parts by weight of Denka Black manufactured by Chemical Industry Co., Ltd., 16 parts by weight of Ketchen Black (Carbon ECP600JD manufactured by LION Co., Ltd.), and an elastomer adhesive (AZ-900 1 manufactured by Nippon Co., Ltd.) 6 weight 3 parts by weight of a part of a tackifier (A10H manufactured by Toagos Co., Ltd.) was mixed and prepared into a slurry for an electrode. An electrode was produced in the same manner as in Example 1 except that the slurry for the electrode was used. When the electrode density and the bending resistance were examined, the electrode density was 0.35 g/cm3, and the bending resistance was evaluated as 〇. A wound battery type capacitor was produced in the same manner as in Example 2 except that this electrode was used. The obtained capacitor was measured in the same manner as in Example 2, and its initial characteristics, low-temperature characteristics, and withstand voltage were measured. The results are shown in Table 1. Example 7 -43- 201142885 100 parts by weight of non-graphitizable activated carbon particles (RPURA, manufactured by KURARAY CHEMICAL Co., Ltd., specific surface area: 1 800 m 2 /g, average particle diameter 8 μηι) activated by steam 3 parts by weight of acetylene black (Denka Black, manufactured by Electric Chemical Industry Co., Ltd.), 16 parts by weight of Ketchen Black (Carbon ECP600JD manufactured by LION Co., Ltd.), and an elastomer binder (manufactured by Nippon Co., Ltd.) AZ-900 1) 6 parts by weight of a heavy-duty and tackified material (10 Η made by East Asian Synthetic Co., Ltd.) was mixed to prepare a slurry for an electrode. An electrode was produced in the same manner as in Example 1 except that the slurry for the electrode was used. When the electrode density and the bending resistance were examined, the electrode density was 0.4 1 g/cm3, and the bending resistance was evaluated as 〇. A wound battery type capacitor was produced in the same manner as in Example 2 except that this electrode was used. The obtained capacitor was measured in the same manner as in Example 2, and its initial characteristics, low-temperature characteristics, and withstand voltage were measured. The results are shown in Table 1. Comparative Example 1 Alkali-activated graphitizable activated carbon particles (NK261 manufactured by KURARAY CHEMICAL Co., Ltd., specific surface area: 2300 m 2 /g, average particle diameter 6 μmη) were used in an amount of 1 part by weight, and acetylene black as a conductive auxiliary agent ( 3 parts by weight of Denka Black manufactured by Electrochemical Industry Co., Ltd., 16 parts by weight of Ketchen Black (Carbon ECP600JD manufactured by LION Co., Ltd.), and elastomer adhesive (AZ-9001, manufactured by Japan ZEON Co., Ltd.) 6 weight 3 parts by weight of a tackifier (A 10H manufactured by Toagos Co., Ltd.) was mixed to prepare a slurry for an electrode. An electrode was produced in the same manner as in Example 1 except that the slurry for the electrode was used. When the electrode density and the bending resistance were examined, the electrode density was -44 - 201142885 0.40 g/cm3, and the bending resistance was evaluated as 〇. A wound battery type capacitor was produced in the same manner as in Example 2 except that this electrode was used. The obtained capacitor was subjected to the characteristics of the period, the low-temperature characteristics, and the withstand voltage in the same manner as in the second embodiment. The results are shown in Table 1 [Table 1], and the system is measured at the beginning -45- 201142885
rH Ο Ο CO ΙΟ 〇S5 1 1 M S« i | 1 〇2 1 1 1 卜 Ο Ο 10 ΙΟ 2^§S CD 寸Ο co ς〇 ISSSS BSS^S ΙΟ ΙΟ Ο C0 ζ〇 255SS5S 侧 寸 ο ο ιο ιη §〇§§§ §S^S§ CO ο ο ιο ιη 〇SS5S^ §»§^« s^His <N ο ο ιη ιο 〇5 w §ssst §§§㈤ mim 踩趣e pIi 丄_ s #ι拗S tn赃运 g g 轿玲 鱗以ss3运⑼§2錄|以§23蒙㈤ss 趣瑚 趣瑚 QUU · · — CO CO 由表1可知,在使用經水蒸氣活化之難石墨化活性碳 粒子之情況時,初期之電特性優良(低電阻),又,維持著 低溫特性,並且可充分地達成長期信賴性。 -46-rH Ο Ο CO ΙΟ 〇S5 1 1 MS« i | 1 〇2 1 1 1 Ο Ο 10 ΙΟ 2^§S CD inch Ο co ς〇ISSSS BSS^S ΙΟ ΙΟ Ο C0 ζ〇255SS5S Side ο ο ιο ι秧§§§§S^S§ CO ο ο ιο ιη 〇SS5S^ §»§^« s^His <N ο ο ιη ιο 〇5 w §ssst §§§(f) mim 踏趣e pIi 丄_ s #ι拗S tn赃运 gg sedan scales to ss3 transport (9) § 2 recorded | to § 23 Meng (five) ss fun Huquu Quu · · — CO CO As can be seen from Table 1, the use of water vapor-activated hard graphitization In the case of activated carbon particles, the initial electrical characteristics are excellent (low resistance), and low-temperature characteristics are maintained, and long-term reliability can be sufficiently achieved. -46-
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