200527454 (1) 九、發明說明 【發明所屬之技術領域】 本發明係有關高強度、高耐熱性、離子傳導性、電解 液保持性優之雙電荷層電容器用分離器，及使用該分離器 之雙電荷層電容器。 【先前技術】 | 將雙電荷層電容器（以下略稱電容器）作大分類時， 可分爲電解液爲水系者，與非水系者。非水電解液電容器 ，與水系電解液電容器比較，由於得到約3倍之能量密度 、，爲現在市售雙電荷層電容器之主流。 電容器用分離器，一直使用由纖維素所成紙製分離器 或由PTFE所成樹脂製分離器。使用非水電解液電容器時 ，分離器含水時，由於關聯電氣特性之惡化，分離器必要 慎重的進行脫水乾燥。由纖維素所成之分離器時，以1 5 0 | °C以上之高溫長時間熱處理時，已知纖維素會碳化，必要 以低於1 5 0 °C溫度乾燥，乾燥時間變長成爲問題。又，由 PTFE所成之分離器時，以去除水分之觀點則無問題，大 型之用途，由於機械強度低操作困難成爲問題。又，由 PTFE所成之分離器，價格高，大量使用之用途推展於現 狀尙無進展。 由此理由，尋求廉價，供給具耐熱性，且機械強度高 操作性優之分離器，日本特開2 0 0 3 2 7 2 9 5 2號公報，提案 使用由耐熱性高分子纖維所成不織布作爲電容器用分離器 -5- 200527454 (2) 。但是’一般不織布容易產生所謂針孔之缺陷，又由於電 解液之保持性低’須將膜厚加厚，不得不將分離器作成雙 層，由於成爲電容器內部電阻上昇之要因，不理想。 【發明內容】 〔發明之揭示〕 如上述現狀尙未發現，能全部滿足耐熱性與機械強度 、離子傳導性、及電解液保持性之分離器，本發明之目的 爲提供能滿足耐熱性、機械強度、離子穿透性全部之雙電 荷層電容器用分離器，及使用該分離器之雙電荷層電容器 〇 本發明者等爲上述課題經深入硏究結果，由芳香族聚 醯胺所成，控制於特定構造之多孔膜，發現可實現耐熱性 、機械強度、離子傳導性、電解液保持性優之雙電荷層電 容器用分離器，完成本發明。 即’本發明，爲由芳香族聚醯胺所成，爲膜厚5〜5 0 # m之多孔膜，該膜之空隙率爲3 0〜8 0 %，且透氣度（ JIS P8117爲基準）爲5〜300秒/1〇〇 mL· in2，且單位 膜厚之刺穿強度爲50 以上爲其特徵之雙電荷層 電容器用分離器。該多空膜內部之平均孔徑以〇.〇1〜5 // m者爲理想，又，該芳香族聚醯胺以噻苯二胺間苯二醯 胺系聚合物爲主成分之聚醯胺者爲理想。又，該多孔膜爲 由芳香族聚醯胺與醯胺系溶劑爲主成分之高分子溶液展流 於支撐物，將該展流物浸漬於含有芳香族非相溶物質之聚 -6- 200527454 (3) 醯胺凝固液，使其微相分離，接著以洗淨、熱處理而製造 者爲理想。 於本發明，雙電荷層電容器之電解液以非水電解液者 爲理想，該非水電解液以溶解銨鹽之電解液者爲理想，該 銨鹽爲使用至少含有1種類非對稱銨鹽者爲理想。該非水 電解液之溶劑爲含比介電率爲1 〇以上之非水溶劑8 0重量 %以上之單獨溶劑或混合溶劑者爲理想，含有80重量％碳 酸酯系溶劑之溶劑更爲理想。 於本發明，雙電荷層電容器之非水電解液可爲含有離 子性液體1 0重量％以上之電解液者。 又，本發明亦包含使用上述分離器之雙電荷層電容器 之發明。 〔用以實施發明之最佳型態〕 以下詳述本發明。又，此等之實施例及說明係爲例示 本發明者，其他之型態不消說亦屬於本發明之範疇。 〔芳香族聚醯胺〕 本發明之聚醯胺，係由芳香族二胺與芳香族二羧酸鹵 化物之聚縮合而得之聚合物。芳香族二胺，具體可列示如 苯二胺、p-苯二胺、L4-二胺基萘、1，5-二胺基萘、1，8_ 一 fe:基萘、2,6 -二胺基萘、2,7 -二胺基萘、3，3·二胺基聯 苯、4,4’-二胺基聯苯、4,4，_二胺基苯醌、3 5 3，-二胺基聯 苯醚、3,4’-二胺基聯苯醚、4,4，_二胺基聯苯醚、3;3，_二 -7- 200527454 (4) 胺基聯苯甲烷、4，4 ’ -二胺基聯苯甲烷、3，3 ’ -二 碼、4,4，-二胺基聯苯碼、3,3’-二胺基聯苯硫化 二胺基聯苯硫化物、4，4 ’ -二胺基聯苯硫醚、1，3 基苯氧基）苯、1，3 -雙（4**胺基苯氧基）本、1 胺基苯氧基）苯、1，4 -雙（4 -胺基苯氧基）苯、 4-胺基苯）乙烷、2,2-雙（4-胺基苯）丙烷等之 胺等。 又，芳香族二羧酸鹵化物可列舉如鄰苯二酸 酸、對苯二酸、1，6-萘二羧酸、1，7-萘二羧酸、 羧酸、2,7-萘二羧酸、3,4’-聯苯二羧酸、4,4’-聯 等之二羧酸鹵化物。此等之二胺、二羧酸鹵化物 用1種類亦可，2種類以上倂用亦可。 於本發明使用之芳香族聚胺，依所得多孔膜 及成本觀點，芳香族二胺以使用間苯二胺、對苯 3，4 ’ -二胺基聯苯醚爲理想，又芳香族二殘酸鹵化 間苯二酸鹵化物、對苯二酸鹵化物爲理想。更理 苯二胺與間苯二酸鹵化物之聚縮合所得聚噻苯二 醯胺。 又，上述芳香族聚醯胺，亦可由己烷二胺、 、十二烷二胺、己撐二胺、六甲撐二羧酸等之二 物，以相對於聚合物之重複單元，20莫耳％以下 聚合。 本發明相關之芳香族聚醯胺，溶解於甲^ 烷酮時，下式（1 )所示之對數黏度，以〇 . 8〜』 胺基聯苯 物、4,4，--雙（3-胺 ，4-雙（3· 雙（ 芳香族二 、間苯二 2,6-萘二 苯二羧酸 各自僅使 之物性面 二胺、或 物以使用 想爲由間 胺間苯二 癸烷二胺 羧酸鹵化 之比例共 S - 2 -吡咯 5 dl/ g， 200527454 (5) 理想爲1·0〜2.2 dl/g之範圍之聚合 低於0.8 dl/g不能得到充分之機械 2.5 dl/g時得到安定的聚合物溶液 到均勻的多孔膜不理想。 對數黏度（單位：dl/g) = In( T :將芳香族聚醯胺〇 . 5 g溶解;! 吡咯烷酮之3 0 °C時毛細管黏度計之流 TO : N-甲基-2-吡咯烷酮之30°C 動時間 C :聚合物溶液中之聚合物濃度 〔芳香族聚醯胺多孔膜〕 本發明之芳香族聚醯胺多孔膜， 特別是，將上述之芳香族聚醯胺溶解 之高分子溶液展流於支撐物，將該展 族非相溶物質之聚醯胺凝固液，使其 淨、熱處理所得之多孔膜之方法（濕 構造之控制性優，且可優生產性製作 理想。 所使用之聚醯胺系溶劑，列舉如 等含有醯胺基之極性醯胺溶劑。 又，展流筒分子溶液之支擦物， 鋼帶、鐵筒、或丙烯、聚對苯二甲酸 薄膜。考慮生產性時，以使用聚合物 物爲理想。對數黏度 強度，對數黏度超過 有困難，由於不能得 T/ TO ) / C ( 1 ) 令 100 mL N -甲基 -2- 動時間 時毛細管黏度計之流 (g/ dL ) 可由任意方法製成。 於聚醯胺系溶劑所得 流物浸漬於含有芳香 微相分離，接著以洗 式微相分離法），膜 本發明之多孔性膜爲 丨N，N-二甲基甲醯胺 可列舉如玻璃基板、 乙二醇酯等之聚合物 薄膜爲理想。此等之 -9- 200527454 (6) 聚合物薄膜亦可施以矽等之脫模處理或電暈放電處理等。 使用醯胺系凝固液之溶劑，具體的可列舉如N-甲基-2-吡咯烷酮、N，N-二甲基乙醯胺、N，N-二甲基甲醯胺。此 等可2種類以上倂用。相對於芳香族聚醯胺之非相溶性物 質’可列舉如水、低級醇、低級醚。此等亦可倂用2種以 上。其中，單獨使用水時，所得多孔膜之膜特性或經濟性 之觀點非常合適。上述醯胺系凝固液中之醯胺溶劑（例如 p 使用100% N-甲基-2-吡咯烷酮時），相對於全體凝固液， 爲4 0重量％〜8 0重量％，理想爲5 0重量％〜7 0重量％， 更理想爲55重量％〜70重量％。醯胺溶劑濃度低於40重 . 量％時，所得多孔膜之機械強度變低不理想，又，濃度超 過 8 0重量％時，由於成爲自立多孔膜之時間費時於生產 性觀點不理想。 凝固之多孔質之展流物移至次洗淨步驟，以水洗淨。 洗淨之多孔質展流物接著以熱處理將水乾燥可得到本發明 B 之多孔膜。又，與熱處理之同時將多孔膜進行延伸，亦可 控制多孔膜之孔構造。 本發明之芳香族聚醯胺多孔膜之膜厚，以5〜5 0 // m 範圍爲其特徵。膜厚低於5 # m時’不僅確保電子之絕緣 性有困難，由於機械強度亦變低操作有困難不理想。又， 膜厚超過5 0 // m時’有利於機械強度，不僅電容器之體 積能量密度降低’由於分離器間之離子傳導性降低不理想 。膜厚之理想範圍爲8〜4 0 # m ’更理想爲1 0〜3 0 # m。 本發明之芳香族聚醯胺多孔膜之空隙率以30〜80%範 -10 - 200527454 (7) Η胃其特徵。空隙率係以多孔體中空隙所佔之比例表示’ 可由以下式（2)算出。 空隙率（％ ) = ( 1 一 p f / Ρ 0 ) X 1 〇 〇 ( 2 ) 使用之合物之真密度 p =多孔膜之假密度 空隙率低於3 0 %時，由於電解液保持性變低，電容器 之內部電阻變高不理想，又，空隙率超過80%時，由於多 p 孔膜之機械強度降低，不僅操作困難，由於內部容易產生 短路不理想。更理想空隙率範圍爲4 0〜7 5 %，更理想爲 50 〜70〇/〇 〇 、 本發明相關之透氣度，係依據JI S P 8 1 1 7爲準之測定 .値。本發明之芳香族聚醯胺多孔膜之透氣度以5〜3 〇〇秒 /100 mL· in2爲其特徵。透氣度大於300秒/100 mL· in2時’多孔之連續構造不充分，由於成爲電容器之內部 電阻上昇之要因不理想。又，透氣度低於5秒/ 1 〇〇 mL · • in2時，由於電容器之自己放電特性下降不理想。透氣度 理想的範圍爲1 0〜2 0 0秒/ 1 0 0 m L · i η2，更理想爲1 5〜 1 5 0 秒 / 1 〇 〇 m L · i η 2 。 本發明之芳香族聚醯胺多孔膜之單位膜厚之刺穿強g 以50 以上者爲其特徵。剌穿強度，爲鋰離子電 池之分離器短路防止強度之表示指標，利用於分離器胃平價 之物性，於本發明依下述條件之測定値作爲單位膜厚之刺 穿強度。 將多孔膜固定於1 1 · 3 m m 0之固定框，將先端半徑 -11 - 200527454 (8) 0.5 m m之針垂直立於多孔膜中央，以2 m m /秒之一定速 度將針壓入，多孔膜開洞時該針所負之力除於多孔膜之膜 厚値爲其刺穿強度。此値低於5 0 mN /// m時，作爲分離 器之強度不充分，電容器組成時短路防止特性不能充分確 保不理想。 本發明之芳香族聚醯胺多孔膜之內部平均孔徑以〇. 〇 1 〜5 # m者爲理想。多孔膜之孔徑可由各種方法規定，本 g 發明將SEM觀察之斷面照相以畫像處理所算出之値爲內 部平均孔徑。詳細之測定方法後述。平均孔徑超過5 // m 時，電容器之電極所使用之活性碳或導電劑脫落時，由於 ， 確可引起內部短路不理想。更理想的平均孔徑範圍爲0.03 〜3 // m。理想爲0.0 5〜2 // m。 〔雙電荷層電容器〕 本發明之雙電荷層電容器，除分極性分離器使用上述 φ 芳香族聚醯胺多孔膜以外，可與向來之雙電荷層電容器同 樣製造。雙電荷層電容器有使用水系電解液、非水電解液 ，本發明之芳香族聚醯胺多孔膜，可適用於任一者之雙電 荷層電容器。但使用非水電解液之雙電荷層電容器，電容 器內部存在水分時，特性容易下降，即對構成材料強烈要 求有效率的去除水分。因應對此非常強的要求，爲本發明 之芳香族聚醯胺多孔膜之最大之特徵，由此觀點，本發明 之芳香族聚醯胺多孔膜更理想適用於使用非水電解液之雙 電荷層電容器。 -12 - 200527454200527454 (1) IX. Description of the invention [Technical field to which the invention belongs] The present invention relates to a separator for an electric double layer capacitor with high strength, high heat resistance, ion conductivity, and excellent electrolyte retention, and a separator using the separator. Electric double layer capacitor. [Prior art] | When the electric double layer capacitors (hereinafter referred to as capacitors) are largely classified, they can be divided into those whose electrolytes are aqueous and those who are not. Compared with water-based electrolytic capacitors, non-aqueous electrolytic capacitors are currently the mainstream of electric double-layer capacitors on the market because they have an energy density of about 3 times. As a separator for a capacitor, a paper separator made of cellulose or a resin separator made of PTFE has been used. When using non-aqueous electrolytic capacitors, when the separator contains water, the separator must be carefully dehydrated and dried due to the deterioration of the related electrical characteristics. When a separator made of cellulose is heat-treated at a high temperature of more than 150 ° C for a long time, it is known that cellulose will be carbonized. It is necessary to dry at a temperature lower than 150 ° C, and the drying time becomes a problem. . In addition, in the case of a separator made of PTFE, there is no problem from the viewpoint of removing moisture, and for large applications, it is a problem due to low mechanical strength and difficult operation. In addition, the separator made of PTFE is expensive and has been used in a large number of applications without progress. For this reason, seeking a separator that is inexpensive, has heat resistance, and has high mechanical strength and excellent operability. Japanese Patent Laid-Open No. 2 0 3 2 7 2 9 5 2 proposes the use of a non-woven fabric made of heat-resistant polymer fibers. As a capacitor separator-5-200527454 (2). However, "Generally, non-woven fabrics are prone to so-called pinhole defects, and because the electrolyte has low retentivity," it is necessary to thicken the film thickness, and the separator has to be double-layered. This is not ideal because it causes the internal resistance of the capacitor to rise. [Summary of the Invention] [Disclosure of the Invention] If the present situation is not found, a separator that can fully satisfy the heat resistance and mechanical strength, ion conductivity, and electrolyte retention is provided. The object of the present invention is to provide a separator that can satisfy the heat resistance and mechanical properties. Separator for electric double layer capacitors having all strength and ion penetrability, and electric double layer capacitor using the same. The inventors of the present invention have conducted intensive investigations on the above-mentioned problems, and are made of aromatic polyamines. A separator for an electric double layer capacitor having excellent heat resistance, mechanical strength, ion conductivity, and electrolyte retention was found in a porous membrane having a specific structure, and the present invention has been completed. That is, the present invention is a porous membrane made of aromatic polyamidamine, with a film thickness of 5 to 50 # m, a porosity of the film of 30 to 80%, and air permeability (based on JIS P8117) It is a separator for electric double layer capacitors characterized by 5 to 300 seconds / 100 mL · in2 and having a puncture strength per unit film thickness of 50 or more. The average pore diameter inside the multi-hollow membrane is preferably from 0.001 to 5 // m, and the aromatic polyamine is a polyamine containing thiophenylenediamine and m-xylylenediamine-based polymer as a main component. Is ideal. In addition, the porous membrane is a polymer solution composed of an aromatic polyamine and a amine-based solvent as a main component, and is spread on a support, and the developed material is immersed in a poly-6-200527454 containing an aromatic incompatible material. (3) The ammonium coagulation liquid is preferably produced by micro-phase separation, followed by washing and heat treatment. In the present invention, the electrolyte of the electric double layer capacitor is preferably a non-aqueous electrolyte, and the non-aqueous electrolyte is preferably an electrolyte that dissolves an ammonium salt. ideal. The solvent of the non-aqueous electrolyte is preferably a non-aqueous solvent with a specific permittivity of 10 or more and a solvent alone or a mixed solvent of 80% by weight or more. A solvent containing 80% by weight of a carbonate-based solvent is more preferable. In the present invention, the non-aqueous electrolyte of the electric double layer capacitor may be an electrolyte containing 10% by weight or more of the ionic liquid. The present invention also includes an invention of an electric double layer capacitor using the above-mentioned separator. [Best Mode for Carrying Out the Invention] The present invention will be described in detail below. In addition, these examples and descriptions are for exemplification of the present inventor, and other types also belong to the scope of the present invention. [Aromatic polyamine] The polyamine of the present invention is a polymer obtained by polycondensation of an aromatic diamine and an aromatic dicarboxylic acid halide. Aromatic diamines, such as phenylenediamine, p-phenylenediamine, L4-diaminonaphthalene, 1,5-diaminonaphthalene, 1,8_ monofe: naphthalene, 2,6-di Amino naphthalene, 2,7-diaminonaphthalene, 3,3 · diaminobiphenyl, 4,4'-diaminobiphenyl, 4,4, -diaminobenzoquinone, 3 5 3,- Diamino diphenyl ether, 3,4'-diamino diphenyl ether, 4,4, _diamino diphenyl ether, 3; 3, _di-7- 200527454 (4) amino diphenyl methane, 4,4'-diaminobiphenylmethane, 3,3'-dicode, 4,4, -diaminobiphenyl code, 3,3'-diaminobiphenylsulfide diaminebiphenylsulfide , 4,4′-diaminobiphenyl sulfide, 1,3-phenylphenoxy) benzene, 1,3-bis (4 ** aminophenoxy) benzyl, 1aminophenoxy) benzene, Amines such as 1,4-bis (4-aminophenoxy) benzene, 4-aminophenyl) ethane, 2,2-bis (4-aminophenyl) propane, and the like. Examples of the aromatic dicarboxylic acid halide include phthalic acid, terephthalic acid, 1,6-naphthalenedicarboxylic acid, 1,7-naphthalenedicarboxylic acid, carboxylic acid, and 2,7-naphthalenedicarboxylic acid. Carboxylic acid, 3,4'-biphenyldicarboxylic acid, 4,4'-bicarboxylic acid and other dicarboxylic acid halides. These diamines and dicarboxylic acid halides may be used singly or in combination of two or more kinds. For the aromatic polyamine used in the present invention, from the viewpoint of the obtained porous film and cost, it is ideal to use m-phenylenediamine and p-benzene 3,4'-diamine diphenyl ether as the aromatic diamine. Acid halogenated isophthalic acid halides and terephthalic acid halides are preferred. Correction Polythiophenylenediamine obtained by polycondensation of phenylenediamine and isophthalic acid halide. In addition, the above-mentioned aromatic polyamidoamine may also be composed of hexanediamine, dodecanediamine, hexamethylenediamine, hexamethylene dicarboxylic acid, and the like, with respect to the repeating unit of the polymer, 20 mol. % Polymerization. When the aromatic polyamidine related to the present invention is dissolved in methylalkanone, the logarithmic viscosity shown by the following formula (1) is expressed in terms of 0.8 ~~ aminobiphenyl, 4,4, --bis (3 -Amine, 4-bis (3 · bis (aromatic di, m-phenylene 2,6-naphthalenedicarboxylic acid) each has only its physical properties, diamine, or m-amine, m-xylylenedidecyl. The proportion of alkanediamine carboxylic acid halogenated total S-2 -pyrrole 5 dl / g, 200527454 (5) Ideally the polymerization in the range of 1.0-2.2 dl / g is less than 0.8 dl / g can not obtain sufficient mechanical 2.5 dl It is not ideal to obtain a stable polymer solution to a homogeneous porous film at / g. Logarithmic viscosity (unit: dl / g) = In (T: dissolve 0.5 g of aromatic polyamidine;! 30 ° C of pyrrolidone Time of capillary viscometer TO: N-methyl-2-pyrrolidone at 30 ° C Dynamic time C: Polymer concentration in polymer solution [Aromatic polyfluorene membrane] The aromatic polyamine porous of the present invention The film, in particular, spreads the polymer solution in which the aromatic polyamide is dissolved on a support, and cleans and heat-treats the polyamide coagulation liquid of the incompatible material in the exhibition. The method of the obtained porous membrane (wet structure is excellent in controllability, and it can be produced with excellent productivity. The polyamine-based solvents used include, for example, polar amine solvents containing amine groups. Also, the molecules of the stretch tube Solution wipes, steel strips, iron cylinders, or acrylic, polyterephthalic acid films. When considering productivity, it is ideal to use polymer materials. Log viscosity strength, it is difficult to exceed the log viscosity, because T / TO) / C (1) Capillary viscometer flow (g / dL) at 100 mL N-methyl-2- dynamic time can be made by any method. The stream obtained in polyamine-based solvent is immersed in the aromatic micro Phase separation, followed by washing microphase separation method), membrane The porous membrane of the present invention is N, N-dimethylformamide, and polymer films such as glass substrates, glycol esters, etc. are ideal. This Etc.-9- 200527454 (6) The polymer film may also be subjected to a release treatment such as silicon or a corona discharge treatment, etc. A solvent using a fluorene-based coagulating solution may be exemplified by N-methyl-2- Pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamidine These can be used in two or more types. For non-compatible substances such as water, lower alcohols, and lower ethers with respect to aromatic polyamines, two or more can be used. Among them, when water is used alone, The viewpoint of membrane characteristics or economics of the obtained porous membrane is very suitable. The amidine solvent in the amidine coagulation solution (for example, when 100% N-methyl-2-pyrrolidone is used for p), it is 4 with respect to the whole coagulation solution. 0 to 80% by weight, preferably 50 to 70% by weight, and more preferably 5 to 70% by weight. When the concentration of the ammonium solvent is less than 40% by weight, the mechanical strength of the obtained porous membrane is not ideal, and when the concentration exceeds 80% by weight, the time required to become a self-supporting porous film is not satisfactory from the viewpoint of productivity. The solidified porous fluid is moved to the second washing step and washed with water. The washed porous spreading material is then dried by heat treatment to obtain a porous film of the present invention B. In addition, by extending the porous film simultaneously with the heat treatment, the pore structure of the porous film can be controlled. The film thickness of the porous aromatic polyamide membrane of the present invention is characterized by a range of 5 to 5 0 // m. When the film thickness is less than 5 #m, it is not only difficult to ensure the insulation of the electrons, but also it is difficult to operate due to the low mechanical strength. In addition, when the film thickness exceeds 5 0 // m, ′ is favorable for mechanical strength, and not only the volume energy density of the capacitor is reduced, but it is not ideal because the ion conductivity between the separators is reduced. The ideal range of the film thickness is 8 to 4 0 # m ′, and more preferably 10 to 3 0 # m. The porosity of the porous aromatic polyamide membrane of the present invention ranges from 30 to 80%. -10-200527454 (7) It is characterized by stomach. The porosity is expressed by the proportion of voids in the porous body, and can be calculated from the following formula (2). Porosity (%) = (1-pf / P 0) X 1 〇〇 (2) True density of the compound used p = False density of porous membrane When the porosity is less than 30%, the electrolyte retention will change Low, the internal resistance of the capacitor becomes undesirably high, and when the porosity exceeds 80%, the mechanical strength of the multi-porous membrane decreases, which is not only difficult to operate, but is also not ideal due to the internal short circuit. A more ideal porosity range is 40 to 75%, and more preferably 50 to 70/00. The air permeability related to the present invention is measured according to JI S P 8 11 17. The air permeability of the porous aromatic polyamide membrane of the present invention is characterized by 5 to 300 seconds / 100 mL · in2. When the air permeability is greater than 300 seconds / 100 mL · in2, the continuous structure of the porous body is insufficient, and it is not ideal because it is a factor that causes the internal resistance of the capacitor to increase. In addition, if the air permeability is less than 5 seconds / 100 mL · • in2, the self-discharge characteristic of the capacitor is not satisfactory. The ideal range of air permeability is 10 to 200 seconds / 100 m L · i η2, and more preferably 15 to 150 seconds / 100 m L · i η 2. The puncture strength g per unit film thickness of the porous aromatic polyamide membrane of the present invention is characterized by 50 or more. The puncture strength is an indicator of the short-circuit prevention strength of the separator of a lithium ion battery. It is used for the physical properties of the separator's stomach. In the present invention, the puncture strength is measured as the unit film thickness. Fix the porous membrane to the 1 1 · 3 mm 0 fixed frame, place the needle with a tip radius of -11-200527454 (8) 0.5 mm vertically at the center of the porous membrane, and press the needle at a certain speed of 2 mm / sec. The force exerted by the needle when opening the membrane is divided by the membrane thickness of the porous membrane, which is its puncture strength. When this value is less than 50 mN /// m, the strength as a separator is not sufficient, and the short-circuit prevention characteristics when the capacitor is formed cannot be sufficiently ensured. The internal average pore diameter of the porous aromatic polyamide membrane of the present invention is preferably 0.001 to 5 # m. The pore diameter of the porous membrane can be specified by various methods. In the present invention, the cross-section of the SEM observation is taken as the average pore diameter calculated by image processing. The detailed measurement method will be described later. When the average pore diameter exceeds 5 // m, when the activated carbon or conductive agent used in the electrode of the capacitor falls off, it may cause an internal short circuit because of. A more ideal average pore size range is 0.03 to 3 // m. The ideal is 0.0 5 ~ 2 // m. [Electric Double-Layer Capacitor] The electric double-layer capacitor of the present invention can be manufactured in the same manner as the conventional electric double-layer capacitor except that the polarizing separator uses the above-mentioned φ aromatic polyamine porous membrane. The electric double layer capacitor includes an aqueous electrolytic solution and a non-aqueous electrolytic solution. The aromatic polyimide porous film of the present invention can be applied to any electric double layer capacitor. However, when an electric double layer capacitor using a non-aqueous electrolyte is used, there is a tendency for the characteristics to deteriorate when moisture is present in the capacitor. That is, the constituent materials are strongly required to remove moisture efficiently. In response to this very strong requirement, this is the biggest feature of the aromatic polyamine porous membrane of the present invention. From this point of view, the aromatic polyamine porous membrane of the present invention is more suitable for double charge using a non-aqueous electrolyte. Layer capacitor. -12-200527454
非水電解液，無特別限制，如通常雙電荷層電宅 者。電解質，陽離子成分可舉例如第4級銨離子或賛 鱗離子，具體的可列舉如四甲基銨離子（Me4N+ )、 基銨離子（Et4N+)、乙基三甲基銨離子（Me3EtN 二甲基二乙基銨離子（Me2Et2N+)、三乙基甲基g (Et3MeN+)、四丙基銨離子（pr4N+)、四丁基g (B υ 4 N )、二丁基甲基鏡離子（Bu3MeN+)、四琴 離子（Me4P+)、四乙基鱗離子（Et4P+)、四丁基_ (Bu4P+ )。又，陰離子成分列舉如四氟硼酸離子（ )、六氟錢酸離子（PF6 —)。此等之陽離子成分 子成分所成之鹽，可單獨使用，或2種類以上混合 其中，特別以銨鹽之電化學安定性、對非水溶劑之 觀點爲理想，更理想爲三乙基甲基銨離子等之非對 又，將此等之電解質溶解之非水溶劑，比介電 1 0以上者爲理想，具體的列舉如碳酸丙烯酯、碳酸 酯、碳酸丁烯酯、碳酸二乙酯、碳酸亞乙烯酯、1，2. 氧乙烷、1，2-二乙氧乙烷、7 -丁內酯、環丁碼、乙腈 此等可單獨使用，亦可2種類以上混合使用。又亦可 比介電率低之溶劑作爲添加劑，此時，以混合80重 以上比介電率爲1 〇以上之溶劑爲理想。 又，非水電解液可使用離子性液體作爲電解質及 電解液使用。此時之離子性液體之含有量，必要含巧 重量％以上。離子性液體之含有量低於1 0重量％時， =器用 ;"及 四乙 f) > 離子 離子 基錢 :離子 BF4 ~ 陰離 用。 解性 銨鹽 率以 乙烯 .二甲 等。 添加 [量％ /或 110 由於 -13 - (10) 200527454 電解液之離子傳導性降低不理想。離子性液體具體的例， 陽離子如如烷基咪唑啉離子、烷基吡啶鑰離子、院基鞍離 子等，一方面，陰離子如四硼酸離子、六氟硫酸鹽、雙贏 甲烷磺醯亞胺等。由此等之陽離子成分與陰離子成分所成 之鹽，可單獨使用，亦可2種類以上混合使用。以離子性 液體作爲電解質使用時，可溶解於上述非水溶劑作爲電解 液。 【實施方式】 以下以實施例詳細說明本發明。但是本發明不限於實 _ 施例。又，多孔膜之測定方法如下。 (1 )空隙率 將乾燥後之多孔膜截切成 A ( mm ) X B ( mm )之大 小，厚度C ( m m )，測定重量D ( g ) ( A、B適當的選 擇）。由上述値以下式求得假密度E。接著求出聚合物之 φ 真密度F，由以下式算出多孔度。 假密度 E = D/ (AxBxC) xl000(g/Clll3) 空隙率=(1 - E / F ) χ 1 0 0 % (2 )透氣率 依據JIS P 81 17，於8·62 kPa之壓力求出100 nlL空 氣穿透之時間。 (3 )刺穿強度 將多孔膜固定於1 1 · 3 m m 0之固定框，將先端半徑 0.5 m m之針垂直立於多孔膜中央，以2 m m /秒之一定速 -14 - (11) (11)200527454 度將針壓入，多孔膜開洞時該針所負之力除於多孔膜之膜 厚値爲其刺穿強度。 (4 )平均孔徑 以分解能力4〜7 mN之掃瞄電子顯微鏡將1萬倍率 觀察之斷面照相顯影1 5 0 x 2 0 0 mm，使用掃瞄器以200萬 畫素/ 30000 mm2之解像度，算出直徑o.oiym以上之各 孔之畫素，將其總合除以孔數求出平均孔面積，以此爲真 圓時之直徑作爲平均孔徑。 (5 )交流電阻 使用1.5 Μ三乙基甲基銨四氟硼酸鹽之碳酸丙烯酯溶 液作爲電解液，使用SUS電極之電池評價。 又本實施例所使用之聚合物，全部爲聚（噻苯二胺間 苯二醯胺）（日本帝人 TECHNOPRODUCTS (股）製「 KONEX」，其對數黏度（IV )，係以NMP ( N-甲基吡咯 烷酮）爲溶劑，聚合物濃度0.5 g/ dL，於30°C溫度測定 爲1.4’又，該聚合物之真密度爲1.335 g/cm3。以下將 其稱爲Konex聚合物。 〔實施例1〕 (1 )將Konex聚合物溶解於二甲基乙醯胺，調整聚 噻苯二胺間苯二醯胺之濃度爲8重量％。將滲雜物展流於 聚丙烯薄膜成爲5 0 // m之厚度。其次將展流物投入於二 甲基乙醯胺55重量％與水45重量％所成之30 °C凝固液20 秒鐘得到凝固膜。將凝固膜由聚丙烯膜剝離，於5 0 °C之 -15- 200527454 (12) 水浴中浸漬10分鐘。其次，將該凝固液於l2〇t 1〇分鐘 ，更於2 7 0 C 1 0分鐘處理而得到聚（嚷苯二胺間苯二醯胺 )之多孔膜。所得之多孔膜之物性如表】所示。 (2 )於2 0 // m鋁箔形成由活性碳（比表面積丨2 〇 〇 m / g)與導電助劑（Getting black)與結著劑（聚四氟 乙嫌）所成之分極性電極。於（1 )所得之多孔膜之兩面 ’由薄片狀電極2片將分極性電極與多孔膜挾緊密合，於 • 2 7 0 °C溫度進行去除水分。該層合物冷卻後，分極性電極 與多孔膜浸漬於1·5 Μ三乙基甲基銨四氟硼酸鹽之碳酸丙 烯酯溶液之電解液，製成銅幣型電容器。測定該電容器之 - 容量時爲1.2F/cm2。 〔實施例2〕 除了滲雜劑之塗敷厚度爲100//m以外，與實施例1 同樣之條件製作多孔膜。所得多孔膜之物性如表1所示。 又，與實施例〗同樣製成銅幣型電容器，測定該電容器之 容量時爲1 .2F/ cm2。 〔實施例3〕 將滲雜劑之濃度爲1 〇重量％，滲雜劑之塗敷厚度爲 1 20 // m以外，與實施例1同樣之條件製作多孔膜。所得 之多孔膜於2 8 0 °C之環境延伸2倍，得到延伸之芳香族聚 醯胺多孔膜。所得之多孔膜之物性如表1所示。除了使用 1 -乙基-3 -甲基咪唑鑰四氟硼酸鹽與碳酸丙烯酯之混合溶 -16- 200527454 (13) 液（重量比3 : 7 )爲電解液以外，與實施例1同樣製成 銅幣型電容器，測定該電容器之容量時爲0.9 F/ cm2。 〔表1〕 實施例 膜厚 空隙率 平均孔徑 剌穿強度 透氣度 交流電阻 (%) (//m) (mN / μχή) (sec / 100 mL · in2) (Ω cm2) 1 11 62 0.35 130 18 0.6 2 25 68 0.50 80 68 1.0 3 20 70 0.65 92 35 0.8The non-aqueous electrolyte is not particularly limited, such as those commonly used in electric double layer electric houses. The electrolyte and the cationic component may include, for example, a fourth-order ammonium ion or a scaly ion. Specific examples include tetramethylammonium ion (Me4N +), ammonium ion (Et4N +), and ethyltrimethylammonium ion (Me3EtN dimethyl). Diethylammonium ion (Me2Et2N +), Triethylmethylg (Et3MeN +), Tetrapropylammonium ion (pr4N +), Tetrabutylg (B υ 4 N), Dibutylmethyl mirror ion (Bu3MeN +), Siqin Ions (Me4P +), Tetraethylscale ion (Et4P +), Tetrabutyl_ (Bu4P +). In addition, the anion components include tetrafluoroborate ion (), hexafluoric acid ion (PF6 —). These cations form The salt formed by the molecular component can be used alone or in a mixture of two or more kinds. Particularly, the electrochemical stability of ammonium salts and non-aqueous solvents are preferable, and non-aqueous solvents such as triethylmethylammonium ion are more preferable. The non-aqueous solvent in which these electrolytes are dissolved is preferably more than 10 or more dielectrics. Specific examples include propylene carbonate, carbonate, butene carbonate, diethyl carbonate, vinylene carbonate, 1,2. Oxyethane, 1,2-diethoxyethane, 7-butyrolactone, cyclobutane, Nitriles can be used alone or in combination of two or more types. Solvents with a lower specific dielectric ratio can also be used as additives. In this case, it is preferable to mix solvents with a specific permittivity of 80 or more. Non-aqueous electrolyte can use ionic liquid as electrolyte and electrolyte. The content of ionic liquid at this time must contain more than 5% by weight. When the content of ionic liquid is less than 10% by weight, = device; " 和 四乙 f) > Ion ion base money: Ion BF4 ~ anion. The rate of dissolving ammonium salt is ethylene, dimethyl and so on. The addition of [amount% / or 110 is not ideal due to the decrease in the ion conductivity of the electrolyte. Specific examples of the ionic liquid include cations such as alkylimidazoline ions, alkylpyridine molybdenum ions, and saddle ion. On the one hand, anions such as tetraborate ion, hexafluorosulfate, and win-win methanesulfonylimide. These salts of the cationic component and the anionic component may be used alone or as a mixture of two or more types. When an ionic liquid is used as the electrolyte, it can be dissolved in the non-aqueous solvent as the electrolytic solution. [Embodiment] Hereinafter, the present invention will be described in detail with examples. However, the present invention is not limited to the embodiments. The measurement method of the porous membrane is as follows. (1) Porosity The dried porous membrane is cut into a size of A (mm) X B (mm), thickness C (m m), and the weight D (g) is determined (A and B are appropriate choices). The pseudo-density E is obtained from the following formula. Next, the true true density F of the polymer is obtained, and the porosity is calculated from the following formula. False density E = D / (AxBxC) xl000 (g / Clll3) Void ratio = (1-E / F) χ 1 0 0% (2) Permeability calculated according to JIS P 81 17, at a pressure of 8.62 kPa Time of 100 nlL air penetration. (3) The puncture strength fixes the porous membrane to a 1 1 · 3 mm 0 fixed frame, and a needle with a tip radius of 0.5 mm stands vertically at the center of the porous membrane at a constant speed of 2 mm / sec. -14-(11) ( 11) 200527454 Press the needle into the hole. When the porous membrane is opened, the force of the needle is divided by the thickness of the porous membrane and its puncture strength. (4) Scanning electron microscope with an average pore size of 4 to 7 mN to develop a photograph of a cross section observed at a magnification of 10,000 x 150 mm, using a scanner at a resolution of 2 million pixels / 30,000 mm2 , Calculate the pixels of each hole with a diameter of o.oiym or more, divide the total number by the number of holes to obtain the average hole area, and use the diameter when it is a true circle as the average hole diameter. (5) AC resistance A 1.5 M triethylmethylammonium tetrafluoroborate propylene carbonate solution was used as the electrolytic solution, and the battery was evaluated using a SUS electrode. In addition, all the polymers used in this example are poly (thiophenylenediamine metaxylylene diamine) ("KONEX" manufactured by Teijin Techno Products (Japan), and its log viscosity (IV) is based on NMP (N-formaldehyde) Pyrrolidone) as a solvent, the polymer concentration was 0.5 g / dL, and the polymer was measured to be 1.4 'at 30 ° C. The true density of the polymer was 1.335 g / cm3. Hereinafter, it is referred to as a Konex polymer. [Example 1 ] (1) The Konex polymer was dissolved in dimethylacetamide, and the concentration of polythiophenylenediamine metaxylylenediamine was adjusted to 8% by weight. The inclusions were spread on the polypropylene film to become 5 0 // m thickness. Secondly, the effluent was put into a 30 ° C coagulation solution of 55% by weight of dimethylacetamide and 45% by weight of water for 20 seconds to obtain a coagulated film. The coagulated film was peeled from the polypropylene film, and -15- 200527454 at 50 ° C (12) Immerse in a water bath for 10 minutes. Next, the coagulation solution is treated at 120 to 10 minutes, and more than 270 C to 10 minutes to obtain poly (pyrylenediamine). M-xylylenediamine) porous membrane. The physical properties of the obtained porous membrane are shown in Table]. (2) Activated carbon (compared to the table) Product 丨 200 m / g) and a conductive electrode (Getting black) and binding agent (polytetrafluoroethylene) made of polar electrodes. The two sides of the porous membrane obtained in (1) from the sheet electrode Two pieces of the polarized electrode and the porous membrane were tightly adhered, and the moisture was removed at a temperature of 270 ° C. After the laminate was cooled, the polarized electrode and the porous membrane were immersed in 1.5 M triethylmethylammonium An electrolytic solution of a tetrafluoroborate propylene carbonate solution was used to make a copper coin capacitor. When the capacity of the capacitor was measured, it was 1.2 F / cm2. [Example 2] The coating thickness except for the dopant was 100 // m Other than that, a porous film was produced under the same conditions as in Example 1. The physical properties of the obtained porous film are shown in Table 1. In addition, a copper coin capacitor was fabricated in the same manner as in Example 1. When the capacitance of the capacitor was measured, it was 1.2 F / cm2. [Example 3] A porous film was prepared under the same conditions as in Example 1 except that the concentration of the dopant was 10% by weight and the coating thickness of the dopant was 1 20 // m. The obtained porous film was prepared at 2 8 The environment at 0 ° C is extended twice, and an extended aromatic polyamine porous membrane is obtained. The physical properties of the porous membrane are shown in Table 1. Except for the use of a mixed solution of 1-ethyl-3 -methylimidazolium tetrafluoroborate and propylene carbonate-16-200527454 (13) solution (weight ratio 3: 7) A copper coin capacitor was fabricated in the same manner as in Example 1 except for the electrolytic solution, and the capacitance of the capacitor was measured to be 0.9 F / cm2. [Table 1] Examples of film thickness, porosity, average pore diameter, puncture strength, air permeability, and AC resistance (%) ( // m) (mN / μχή) (sec / 100 mLin2) (Ω cm2) 1 11 62 0.35 130 18 0.6 2 25 68 0.50 80 68 1.0 3 20 70 0.65 92 35 0.8
〔產業上之利用領域〕 依本發明，兼備所有優耐熱性與機械強度、高離子傳 導性與電解液保持性，可提供爲雙電荷層電容器用分離器 。由使用該分離器，由於可於高溫將水分去除，與分極性 電極同時熱處理，生產性大幅提高，又由於可抑低水分之 混入，得到耐久性優之雙電荷層電容器。又，由於機械性 優，膜厚可薄，可得到內部電阻低’且能量密度高之雙電 荷層電容器。 -17 -[Application fields in the industry] According to the present invention, all of excellent heat resistance and mechanical strength, high ion conductivity and electrolyte retention can be provided, and it can be provided as a separator for electric double layer capacitors. By using this separator, the moisture can be removed at high temperature, and the polarized electrode can be heat-treated at the same time, the productivity is greatly improved, and the inclusion of low moisture can be suppressed to obtain an electric double layer capacitor with excellent durability. In addition, due to its excellent mechanical properties, the film thickness can be reduced, and a double-layer capacitor having a low internal resistance and a high energy density can be obtained. -17-