TWI445026B - A collector for an electric double layer capacitor ,an electrode for an electric double layer capacitor ,electrilytic double layered capacitor and method of producing them - Google Patents
A collector for an electric double layer capacitor ,an electrode for an electric double layer capacitor ,electrilytic double layered capacitor and method of producing them Download PDFInfo
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本發明係關於一種電雙層電容器用集電體、電雙層電容器用電極、及電雙層電容器及其等之製造方法。The present invention relates to a current collector for an electric double layer capacitor, an electrode for an electric double layer capacitor, an electric double layer capacitor, and the like.
電雙層電容器係可急速充放電，充放電過強，不伴隨化學反應，故壽命長，可在廣溫度範圍使用，又，因不含重金屬，環境優等具有電池所無之特性。電雙層電容器主要使用於記憶體支援電源等。進一步，電雙層電容器係亦被研究活用於與太陽電池或燃料電池組合之電力貯存系統、油汽混合車之引擎輔助等。The electric double-layer capacitor can be rapidly charged and discharged, and the charge and discharge are too strong, and the chemical reaction is not accompanied. Therefore, the life is long, and it can be used in a wide temperature range. Moreover, since it does not contain heavy metals, the environment is excellent and has characteristics not possessed by the battery. Electric double layer capacitors are mainly used for memory support power supplies and the like. Further, the electric double layer capacitor system has also been studied for use in a power storage system combined with a solar cell or a fuel cell, an engine assist of an oil-gas hybrid vehicle, and the like.
電雙層電容器係使含有活性碳等之合劑層合於鋁箔等的集電體而構成的一對分極性電極，在含有電解質離子之溶液中介由分隔膜而對向之構造所構成。若對電極施加直流電壓，於正(+)側分極之電極，係拉引溶液中之陰離子，於負(-)側分極之電極係拉引溶液中之陽離子。藉此，可利用於電極與溶液之界面所形成之電雙層作為電能。The electric double layer capacitor is a structure in which a pair of polar electrodes including a mixture of activated carbon and the like are laminated on a current collector such as an aluminum foil, and a solution containing electrolyte ions is interposed by a separator. If a DC voltage is applied to the electrode, the electrode in the positive (+) side electrode pulls the anion in the solution, and the negative (-) side electrode pulls the cation in the solution. Thereby, an electric double layer formed by the interface between the electrode and the solution can be utilized as electric energy.
為得到高輸出高容量之電雙層電容器，必須儘可能地減少電容器具有之內部電阻。電容器之內部電阻已知係藉由電解液、分極性電極、集電體或此等之界面等所產生，例如，以減少集電體或電極具有之體積電阻值，俾減少電容器之內部電阻之嘗試自以往即已被實施。In order to obtain an electric double layer capacitor with high output and high capacity, it is necessary to reduce the internal resistance of the capacitor as much as possible. The internal resistance of the capacitor is known to be generated by an electrolyte, a polarity-differential electrode, a current collector, or the like, for example, to reduce the volume resistance of the current collector or the electrode, and to reduce the internal resistance of the capacitor. The attempt has been implemented since the past.
專利文獻1中係已揭示厚10~50μm之鋁箔、厚 0.2~20μm之導電層、及厚80~500μm之電極層以此順序所層合之電雙層電容器用電極。此導電層係由含有石墨粉末作為導電材及含有聚醯胺醯亞胺樹脂作為黏結劑之導電性塗料所構成。Patent Document 1 discloses that aluminum foil having a thickness of 10 to 50 μm is thick. An electrode for an electric double layer capacitor in which the conductive layer of 0.2 to 20 μm and the electrode layer of 80 to 500 μm are laminated in this order. The conductive layer is composed of a conductive coating containing graphite powder as a conductive material and a polyamidoximine resin as a binder.
專利文獻1：特開2002-270470號公報Patent Document 1: JP-A-2002-270470
專利文獻2係揭示一種電雙層電容器用電極，其係於電極集電體上含有比表面積100~2500m2 /g之碳極料的電極層，與導電性高於前述電極層且多孔質之高導電層以此順序所層合而構成。Patent Document 2 discloses an electrode for an electric double layer capacitor which is an electrode layer containing a carbon electrode having a specific surface area of 100 to 2500 m 2 /g on an electrode current collector, and having a conductivity higher than that of the electrode layer and having a porous state The highly conductive layers are laminated in this order.
使用一含碳之導電性接著劑而貼合於電極集電體上含有比表面積100~2500m2 /g之碳極料的電極層而接合已被記載。The electrode layer which is bonded to the electrode current collector and contains a carbon electrode having a specific surface area of 100 to 2500 m 2 /g is bonded using a carbon-containing conductive adhesive.
專利文獻2：特開2003-309045號公報Patent Document 2: JP-A-2003-309045
又，專利文獻3中係已揭示一種電雙層電容器用集電體，其係由導電劑與熱塑性樹脂所構成之薄膜，與設於該薄膜表面之低電阻層所構成。Further, Patent Document 3 discloses a current collector for an electric double layer capacitor which is composed of a film made of a conductive agent and a thermoplastic resin, and a low resistance layer provided on the surface of the film.
專利文獻3：特開2004-31468號公報Patent Document 3: JP-A-2004-31468
但，含有於上述公報所提出者，且以往之電雙層電容器係內部阻抗比較大，且就急速充發電而言不能滿足。However, it is included in the above-mentioned publication, and the conventional electric double layer capacitor has a relatively large internal impedance and cannot be satisfied in terms of rapid charge generation.
本發明係有鑑於上述事情者，目的在於提供一種低阻抗且高電容，可以高的充放電電流急速充放電，用以得到高性能之電雙層電容器的電雙層電容器用集電體、電雙層電容器用電極、以及其等之製造方法。The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a collector and an electric double layer capacitor for low-impedance and high-capacitance, which can be rapidly charged and discharged with a high charge/discharge current for obtaining a high-performance electric double-layer capacitor. An electrode for a double layer capacitor, and a method of manufacturing the same.
本發明人等係為達成上述目的，經累積專心研究之結果發現，活用離子透過性化合物以取代至今所使用之黏結劑化合物，具體上係於電雙層電容器用之以往集電體(鋁箔等)上，合併具有離子透過性與導電性之皮膜，更具體係藉由形成含有離子透過性化合物與碳微粒子a之皮膜a，可得到以低阻抗且高電容，並可急速充放電之電雙層電容器。In order to achieve the above object, the inventors of the present invention have found that the ion-permeable compound is used in place of the binder compound used so far, and is specifically used for the conventional current collector for an electric double-layer capacitor (aluminum foil, etc.). On the other hand, a film having ion permeability and conductivity is combined, and by forming a film a containing an ion-permeable compound and carbon particles a, a double electrode having low impedance and high capacitance and rapidly charging and discharging can be obtained. Layer capacitor.
本發明係依據此見識，進一步進行研究而終完成者。亦即，本發明係提供以下之解決手段。The present invention is based on this knowledge and is further studied and completed. That is, the present invention provides the following solutions.
[1].一種電雙層電容器用集電體，係具有導電性薄片、與於其上具備之含有離子透過性化合物及碳微粒子a之皮膜a。[1] A current collector for an electric double layer capacitor comprising a conductive sheet and a film a containing an ion permeable compound and carbon fine particles a.
[2].如[1]項之電雙層電容器用集電體，其中導電性薄片為鋁箔、鋁蝕刻箔或鋁沖壓箔。[2] The current collector for an electric double layer capacitor according to [1], wherein the conductive sheet is an aluminum foil, an aluminum etched foil or an aluminum stamped foil.
[3].如[1]或[2]項之電雙層電容器用集電體，其中離子透過性化合物為對有機溶劑無膨潤性之化合物。[3] The current collector for an electric double layer capacitor according to [1] or [2], wherein the ion permeable compound is a compound which is non-swellable to an organic solvent.
[4].如[1]~[3]項中任一項之電雙層電容器用集電體，其中離子透過性化合物為於有機溶劑之摩擦剝離試驗中不產生剝離之化合物。[4] The current collector for an electric double layer capacitor according to any one of [1] to [3] wherein the ion permeable compound is a compound which does not cause peeling in a friction peeling test of an organic solvent.
[5].如[1]~[4]項中任一項之電雙層電容器用集電體，其中離子透過性化合物係氟離子之透過度為1×10－ 2 S/cm以上。[5] The current collector for an electric double layer capacitor according to any one of [1] to [4] wherein the ion-permeable compound has a transmittance of fluorine ions of 1 × 10 - 2 S/cm or more.
[6].如[1]~[5]項中任一項之電雙層電容器用集電體，其中離子透過性化合物係平均分子量為5萬以下。[6] The current collector for an electric double layer capacitor according to any one of [1] to [5] wherein the ion-permeable compound has an average molecular weight of 50,000 or less.
[7].如[1]~[6]項中任一項之電雙層電容器用集電體，其中離子透過性化合物為多糖類或為使多糖類交聯之化合物。[7] The current collector for an electric double layer capacitor according to any one of [1] to [6] wherein the ion permeable compound is a polysaccharide or a compound which crosslinks the polysaccharide.
[8].如[1]~[6]項中任一項之電雙層電容器用集電體，其中離子透過性化合物為使多糖類以丙烯醯胺、丙烯腈、甲殼素吡咯烷酮羧酸鹽、羥基丙基甲殼素、酞酸酐、馬來酸酐、偏苯三甲酸酐、均苯四甲酸酐、酸酐之任一者而交聯的化合物。[8] The current collector for an electric double layer capacitor according to any one of [1] to [6] wherein the ion permeable compound is a polysaccharide such as acrylamide, acrylonitrile or chitin pyrrolidone carboxylate. A compound which is crosslinked by any of hydroxypropyl chitin, phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, or an acid anhydride.
[9].如[7]或[8]項之電雙層電容器用集電體，其中多糖類為甲殼素或幾丁質。[9] The current collector for an electric double layer capacitor according to [7] or [8], wherein the polysaccharide is chitin or chitin.
[10].如[1]~[9]項中任一項之電雙層電容器用集電體，其中皮膜a在膠帶剝離試驗(JIS DO202－1988)中不剝離。[10] The current collector for an electric double layer capacitor according to any one of [1] to [9], wherein the film a is not peeled off in a tape peeling test (JIS DO202-1988).
[11].如[1]~[10]項中任一項之電雙層電容器用集電體，其中皮膜a為藉熱硬化所得者。[11] The current collector for an electric double layer capacitor according to any one of [1] to [10] wherein the film a is obtained by heat hardening.
[12].如[1]~[11]項中任一項之電雙層電容器用集電體，其中於皮膜a進一步含有活性碳a。[12] The current collector for an electric double layer capacitor according to any one of [1] to [11] wherein the film a further contains activated carbon a.
[13].如[1]~[12]項中任一項之電雙層電容器用集電體，其中碳微粒子a為針狀或棒狀。[13] The current collector for an electric double layer capacitor according to any one of [1] to [12] wherein the carbon microparticles a are needle-shaped or rod-shaped.
[14].一種電雙層電容器用電極，其係具有如[1]~[13]項中任一項的電雙層電容器用集電體、與於該集電體之皮膜a上所具備的含有黏結劑、碳微粒子b及活性碳b之皮膜b。[14] The electrode for an electric double layer capacitor according to any one of [1] to [13], wherein the current collector for the electric double layer capacitor is provided on the film a of the current collector The film b containing a binder, carbon particles b and activated carbon b.
[15].如[14]項之電雙層電容器用電極，其中碳微粒子b為針狀或棒狀。[15] The electrode for an electric double layer capacitor according to [14], wherein the carbon microparticles b are needle-shaped or rod-shaped.
[16].如[14]或[15]項之電雙層電容器用電極，其中活性碳b係BET比表面積為800~2500m2 /g。[16] The electrode for an electric double layer capacitor according to [14] or [15], wherein the activated carbon b has a BET specific surface area of 800 to 2500 m 2 /g.
[17].如[14]~[16]項中任一項之電雙層電容器用電極，其中黏結劑含有離子透過性化合物。[17] The electrode for an electric double layer capacitor according to any one of [14] to [16] wherein the binder contains an ion permeable compound.
[18].一種電雙層電容器用集電體之製造方法，其係包含如下步驟：將使離子透過性化合物、碳微粒子a分散或溶解於溶劑者，塗布於導電性薄片，再乾燥而形成皮膜a 之步驟。[18] A method for producing a current collector for an electric double layer capacitor, comprising the steps of dispersing or dissolving an ion-permeable compound or carbon fine particles a in a solvent, applying the conductive sheet, and drying the film. The step of the film a .
[19].如[18]項之電雙層電容器用集電體之製造方法，其中離子透過性化合物係氟離子之透過度為1×10－ 2 S/cm以上。[19] The electric double layer capacitor [18] The method of manufacturing a collector, wherein the fluorine-based ion-permeable compound ions permeability of 1 × 10 -. 2 S / cm or more.
[20].如[18]或[19]項之電雙層電容器用集電體之製造方法，其中離子透過性化合物係平均分子量為5萬以下。[20] The method for producing a current collector for an electric double layer capacitor according to [18] or [19], wherein the ion-permeable compound has an average molecular weight of 50,000 or less.
[21].如[18]~[20]項中任一項之電雙層電容器用集電體之製造方法，其中離子透過性化合物為多糖類或為使多糖類交聯之化合物。[21] The method for producing a current collector for an electric double layer capacitor according to any one of [18] to [20] wherein the ion permeable compound is a polysaccharide or a compound for crosslinking a polysaccharide.
[22].如[18]~[20]項中任一項之電雙層電容器用集電體之製造方法，其中離子透過性化合物為使多糖類以丙烯醯胺、丙烯腈、甲殼素吡咯烷酮羧酸鹽、羥基丙基甲殼素、酞酸酐、馬來酸酐、偏苯三甲酸酐、均苯四甲酸酐、酸酐之任一者而交聯的化合物。[22] The method for producing a current collector for an electric double layer capacitor according to any one of [18] to [20] wherein the ion permeable compound is a polysaccharide such as acrylamide, acrylonitrile or chitin pyrrolidone. A compound which is crosslinked by any one of a carboxylate, hydroxypropyl chitin, phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, or an acid anhydride.
[23].如[18]~[22]項中任一項之之電雙層電容器用集電體之製造方法，其中碳微粒子a為針狀或棒狀。[23] The method for producing a current collector for an electric double layer capacitor according to any one of [18], wherein the carbon microparticles a are needle-shaped or rod-shaped.
[24].一種電雙層電容器用電極之製造方法，其係包含如下步驟：將使黏結劑、碳微粒子b與活性碳b分散或溶解於溶劑者，塗布於如[1]~[13]項中任一項之之電雙層電容器用集電體之皮膜a上，再乾燥而形成皮膜b之步驟。[24] A method for producing an electrode for an electric double layer capacitor, comprising the steps of dispersing or dissolving a binder, carbon fine particles b and activated carbon b in a solvent, and applying it to [1] to [13]. In the film a of the current collector for the electric double layer capacitor according to any one of the above items, the film b is further dried to form the film b.
[25].一種電雙層電容器用電極之製造方法，其係包含如下步驟：將使離子透過性化合物、碳微粒子a分散或溶解於溶劑者，塗布於導電性薄片，再乾燥而形成皮膜a；將使黏結劑、碳微粒子b與活性碳b分散或溶解於溶劑者，塗布皮膜a上，再乾燥而形成皮膜b之步驟。[25] A method for producing an electrode for an electric double layer capacitor, comprising the steps of dispersing or dissolving an ion-permeable compound or carbon fine particles a in a solvent, applying the conductive sheet, and drying the film to form a film a The step of dispersing or dissolving the binder, the carbon fine particles b and the activated carbon b in the solvent, coating the film a, and drying to form the film b.
[26].如[25]項之電雙層電容器用電極之製造方法，其中離子透過性化合物係氟離子之透過度為1×10－ 2 S/cm以上。[26] The electric double layer capacitor [25] The method for producing items of electrodes, wherein the fluorine-based ion-permeable compound ions permeability of 1 × 10 -. 2 S / cm or more.
[27].如[25]或[26]項之電雙層電容器用電極之製造方法，其中離子透過性化合物係平均分子量為5萬以下。[27] The method for producing an electrode for an electric double layer capacitor according to [25] or [26], wherein the ion-permeable compound has an average molecular weight of 50,000 or less.
[28].如[25]~[27]項中任一項之電雙層電容器用電極之製造方法，其中離子透過性化合物為多糖類或為使多糖類交聯之化合物。The method for producing an electrode for an electric double layer capacitor according to any one of the items [25], wherein the ion-permeable compound is a polysaccharide or a compound for crosslinking a polysaccharide.
[29].如[25]~[28]項中任一項之電雙層電容器用電極之製造方法，其中離子透過性化合物為使多糖類以丙烯醯胺、丙烯腈、甲殼素吡咯烷酮羧酸鹽、羥基丙基甲殼素、酞酸酐、馬來酸酐、偏苯三甲酸酐、均苯四甲酸酐、酸酐之任一者而交聯的化合物。[29] The method for producing an electrode for an electric double layer capacitor according to any one of [25] to [28] wherein the ion permeable compound is a polysaccharide such as acrylamide, acrylonitrile or chitin pyrrolidone carboxylic acid. A compound which is crosslinked by any of a salt, hydroxypropyl chitin, phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, or an acid anhydride.
[30].如[25]~[29]項中任一項之之電雙層電容器用電極之製造方法，其中碳微粒子a為針狀或棒狀。[30] The method for producing an electrode for an electric double layer capacitor according to any one of [25] to [29] wherein the carbon microparticles a are needle-shaped or rod-shaped.
[31].如[24]~[30]項中任一項之之電雙層電容器用電極之製造方法，其中碳微粒子b為針狀或棒狀。[31] The method for producing an electrode for an electric double layer capacitor according to any one of [24], wherein the carbon microparticles b are needle-shaped or rod-shaped.
[32].如[24]~[31]項中任一項之電雙層電容器用電極之製造方法，其中活性碳b係BET比表面積為800~2500m2 /g。[32] The method for producing an electrode for an electric double layer capacitor according to any one of [24] to [31] wherein the activated carbon b has a BET specific surface area of 800 to 2500 m 2 /g.
[33].一種電雙層電容器，其係具備如[14]~[17]項中任一項之電雙層電容器用電極、分隔膜與電解液。[33] An electric double layer capacitor comprising the electrode for an electric double layer capacitor according to any one of [14] to [17], a separator film, and an electrolytic solution.
[34].如[33]項之電雙層電容器，其中電雙層電容器為層合型或捲繞型。[34] The electric double layer capacitor of [33], wherein the electric double layer capacitor is a laminated type or a wound type.
[35].一種電雙層電容器之製造方法，其係包含如下步驟：使如[14]~[17]項中任一項之電雙層電容器用電極與分隔膜重疊之步驟；使重疊之電極及分隔膜浸漬於電解液之步驟。[35] A method of manufacturing an electric double layer capacitor, comprising the steps of: superposing an electrode for an electric double layer capacitor according to any one of [14] to [17] and a separator; The step of immersing the electrode and the separator film in the electrolyte.
[36].一種電源系統，其係含有如[33]或[34]項之電雙層電容器。[36] A power supply system comprising an electric double layer capacitor as in [33] or [34].
[37].一種汽車，其係使用如[33]或[34]項之電雙層電容器。[37] A car using an electric double layer capacitor such as [33] or [34].
[38].一種火車，其係使用如[33]或[34]項之電雙層電容器。[38] A train using an electric double layer capacitor such as [33] or [34].
[39].一種船舶，其係使用如[33]或[34]項之電雙層電容器。[39] A ship using an electric double layer capacitor as in [33] or [34].
[40].一種飛機，其係使用如[33]或[34]項之電雙層電容器。[40]. An aircraft using an electric double layer capacitor as in [33] or [34].
[41].一種攜帶機器，其係使用如[33]或[34]項之電雙層電容器。[41]. A portable machine using an electric double layer capacitor such as [33] or [34].
[42].一種事務機，其係使用如[33]或[34]項之電雙層電容器。[42] A transaction machine using an electric double layer capacitor such as [33] or [34].
[43].一種太陽能電池發電系統，其係使用如[33]或[34]項之電雙層電容器。[43] A solar cell power generation system using an electric double layer capacitor as in [33] or [34].
[44].一種風力發電系統，其係使用如[33]或[34]項之電雙層電容器。[44] A wind power generation system using an electric double layer capacitor as in [33] or [34].
[45].一種通訊機器，其係使用如[33]或[34]項之電雙層電容器。[45] A communication machine using an electric double layer capacitor such as [33] or [34].
[46].一種電子標籤，其係使用如[33]或[34]項之電雙層電容器。[46]. An electronic tag using an electric double layer capacitor as in [33] or [34].
又，在本說明書中表示「x以上」及「y以下」時係包含其邊界值x及y。表示「未達x」及「超過y」時係不含其邊界值x及y。又，以「x~y」所示之範圍的邊界值x及y係包含其範圍。In addition, in the present specification, "x or more" and "y or less" are included, and the boundary values x and y are included. Indicates that "not x" and "exceeded y" do not contain their boundary values x and y. Further, the boundary values x and y of the range indicated by "x~y" include the range.
本發明中之電雙層電容器用集電體、使用於該集電體設有電極層(皮膜b)之電雙層電容器用電極的電雙層電容器，可以低阻抗且高電容，並以高的充放電電流急速充放電。The electric double layer capacitor for an electric double layer capacitor according to the present invention and the electric double layer capacitor for an electric double layer capacitor electrode provided with the electrode layer (film b) in the current collector can have low impedance and high capacitance, and can be high The charge and discharge current is rapidly charged and discharged.
藉由本發明中之製造方法，可容易地得到上述電雙層電容器用集電體、電雙層電容器用電極及電雙層電容器。According to the production method of the present invention, the current collector for an electric double layer capacitor, the electrode for an electric double layer capacitor, and an electric double layer capacitor can be easily obtained.
本發明較佳之實施態樣中的電雙層電容器用集電體，係具有導電性薄片、與於其上具備之含有離子透過性化合物及碳微粒子a之皮膜a。A current collector for an electric double layer capacitor according to a preferred embodiment of the present invention has a conductive sheet and a film a containing an ion permeable compound and carbon fine particles a.
構成本發明之較佳的實施態樣中之集電體用電雙層電容器用集電體的導電性薄片，不僅為未開孔之箔，包含如沖壓金屬箔或網之開孔的箔等。導電性薄片係只要為以導電性材料所構成者即可，並無特別限制，而可舉例導電性金屬製者或導電性樹脂製者。尤其可舉例如鋁製、鋁合金製者。鋁箔一般可使用A1085材、A3003材等之箔。The conductive sheet constituting the current collector for an electric double layer capacitor for a current collector according to a preferred embodiment of the present invention is not only an unopened foil but also a foil such as a punched metal foil or a mesh opening. The conductive sheet is not particularly limited as long as it is made of a conductive material, and examples thereof include a conductive metal or a conductive resin. In particular, for example, aluminum or aluminum alloys can be used. A foil of A1085 material, A3003 material or the like can be generally used for the aluminum foil.
導電性薄片係可為表面平滑者，但適宜藉電性或化學性蝕刻處理等而表面被粗面化者(蝕刻箔)。The conductive sheet may be a smooth surface, but it is suitable for the surface to be roughened by an electrical or chemical etching treatment (etching foil).
導電性薄片係不受厚度而特別限制，但一般宜為5μm~100μm者。若厚度太薄，機械性強度不足，易產生導電性薄片之破裂等。反之，若厚度太厚，電雙層電容器之體積中的導電性薄片占有之體積浪費地變大，電容器之每一體積的電容量易變低。The conductive sheet is not particularly limited in thickness, but is generally preferably 5 μm to 100 μm. If the thickness is too thin, the mechanical strength is insufficient, and cracking of the conductive sheet or the like is liable to occur. On the other hand, if the thickness is too thick, the volume occupied by the conductive sheets in the volume of the electric double layer capacitor is wastefully increased, and the capacitance of each volume of the capacitor is apt to become low.
構成本發明之較佳的實施態樣中之集電體的皮膜a’係含有碳微粒子a、與離子透過性化合物者。The film a' constituting the current collector in the preferred embodiment of the present invention contains carbon fine particles a and an ion permeable compound.
本發明所使用之碳微粒子a係以碳作為主構成成分之導電性微粒子。碳微粒子a係適宜為乙炔黑、Kechen黑、氣相法碳纖維、石墨(黑鉛)等。The carbon fine particles a used in the present invention are conductive fine particles having carbon as a main constituent component. The carbon microparticles a are suitably acetylene black, Kechen black, fumed carbon fiber, graphite (black lead) or the like.
碳微粒子a係宜粉體之電阻就100%之壓粉體為1×10-1 Ω．cm以下者。碳微粒子a係可一種單獨或組合2種以上而使用。The carbon microparticles a are suitable for the powder. The 100% powder is 1 × 10 -1 Ω. Below cm. The carbon microparticles a may be used alone or in combination of two or more.
碳微粒子a係不受其粒子大小而特別限制，但宜體積基準之平均粒徑為10nm~50μm者，更宜為10nm~100nm者。The carbon microparticles a are not particularly limited in their particle size, but the volume average particle diameter is preferably 10 nm to 50 μm, more preferably 10 nm to 100 nm.
碳微粒子a係亦可形狀為球狀者，但宜為針狀或棒狀者(異方形狀者)。異方形狀之碳微粒子a係每一重量之表面積大，與導電性薄片或後述之活性碳b等的接觸面積變大，故即使為少量之添加量，亦可提昇鋁箔與活性碳b間之導電性。異方形狀之碳微粒子a係可舉例如碳奈來管或碳奈米纖維。碳奈來管或碳奈米纖維係纖維徑一般為0.001~0.5μm，宜為0.003~0.2μm，纖維長一般為1~100μm，較佳係1~30μm者，在導電性提昇中適宜。又，可使金屬碳化物或金屬氮化物等之導電性微粒子與碳微粒子a併用。The carbon microparticles a may have a spherical shape, but it is preferably a needle shape or a rod shape (a shape of a foreign shape). The carbon microparticles a of the irregular shape have a large surface area per weight, and have a large contact area with the conductive sheet or the activated carbon b to be described later. Therefore, even if a small amount is added, the aluminum foil and the activated carbon b can be raised. Electrical conductivity. The carbon microparticles a in the form of an alien shape may, for example, be a carbon nanotube or a carbon nanofiber. The diameter of the carbon nanotube or carbon nanofiber fiber is generally 0.001 to 0.5 μm, preferably 0.003 to 0.2 μm, and the fiber length is generally 1 to 100 μm, preferably 1 to 30 μm, which is suitable for conductivity improvement. Further, conductive fine particles such as metal carbide or metal nitride can be used in combination with the carbon fine particles a.
在本發明所使用離子透過性化合物係只要為具有離子可透過之性能者即可，並無特別限制。The ion-permeable compound to be used in the present invention is not particularly limited as long as it has ion-permeable properties.
離子透過性化合物係宜為離子透過度大者。具體上，宜氟離子透過度具有1×10-2 S/cm以上之化合物。氟離子透過度可如以下做法而求得。使離子透過性化合物溶解於水或正甲基吡咯烷酮，進行黏度調整，而塗布於基材，乾燥，空氣環境下在150℃下放置5分鐘而得到薄膜(離子透過膜)。從基材剝離薄膜，測定厚d[μm]。如圖3所示般，於內尺寸之直徑6cm、深度7.5cm之玻璃格室充滿溫度25℃、電傳導度σ0 [S/cm]之純水212cm3 ，以前述薄膜密封玻璃格室。使溫度25℃、濃度0.005質量%之氟化氫的水溶液3.18cm3 (直徑4.5cm、高度2mm)於前述薄膜之表面以接觸面積15.9cm2 接觸60秒鐘。然後，從玻璃格室拿掉薄膜，測定玻璃格室中之純水的電傳導度σ1 [S/cm]。從密封時之純水的電傳導度σ0 、與接觸於氟化氫水溶液後的純水之電傳導度σ1 ，依下式，求出離子透過度T[S/cm]。The ion permeable compound is preferably one having a large ion permeability. Specifically, it is preferred that the fluorine ion permeability has a compound of 1 × 10 -2 S/cm or more. The fluoride ion permeability can be obtained as follows. The ion-permeable compound was dissolved in water or n-methylpyrrolidone, and the viscosity was adjusted, applied to a substrate, dried, and left at 150 ° C for 5 minutes in an air atmosphere to obtain a film (ion permeable film). The film was peeled off from the substrate, and the thickness d [μm] was measured. As shown in Fig. 3, a glass cell having a diameter of 6 cm and a depth of 7.5 cm was filled with a temperature of 25 ° C and an electric conductivity of σ 0 [S/cm] of 212 cm 3 , and the glass cell was sealed with the film. An aqueous solution of hydrogen fluoride having a temperature of 25 ° C and a concentration of 0.005 mass% of 3.18 cm 3 (diameter: 4.5 cm, height: 2 mm) was contacted on the surface of the film at a contact area of 15.9 cm 2 for 60 seconds. Then, the film was taken out from the glass cell, and the electrical conductivity σ 1 [S/cm] of the pure water in the glass cell was measured. From the electrical conductivity σ 0 of the pure water at the time of sealing and the electrical conductivity σ 1 of the pure water after contact with the aqueous hydrogen fluoride solution, the ion permeability T [S/cm] was determined according to the following formula.
T＝(σ1 －σ0 )xd/0.1T=(σ 1 -σ 0 )xd/0.1
又，離子透過性化合物宜數目平均分子量為5萬以下者。Further, the ion-permeable compound preferably has a number average molecular weight of 50,000 or less.
本發明所使用之離子透過性化合物係宜對於有機溶劑無膨潤性之化合物。又，本發明所使用之離子透過性化合物係宜在以有機溶劑所進行的摩擦剝離試驗中不產生剝離之化合物。有時於電雙層電容器之電解液中使用有機溶劑，故宜不受電解液而皮膜膨潤或溶解。The ion-permeable compound used in the present invention is preferably a compound which is not swellable to an organic solvent. Further, the ion-permeable compound used in the present invention is preferably a compound which does not cause peeling in a friction peeling test by an organic solvent. Occasionally, an organic solvent is used in the electrolyte of the electric double layer capacitor, so it is preferred that the film is not swollen or dissolved without being affected by the electrolyte.
又，對有機溶劑之膨潤性係將離子透過性化合物之膜浸漬於用於電解液之有機溶劑(30℃)60分鐘，判斷是否膨潤。Further, in the swelling property of the organic solvent, the film of the ion-permeable compound was immersed in an organic solvent (30 ° C) for an electrolytic solution for 60 minutes, and it was judged whether or not it was swollen.
以有機溶劑所進行的摩擦剝離試驗係使離子透過性化合物之膜表面以用於電解液之有機溶劑浸入之布，加上100g重之力而擦拭10次，觀察膜是否剝離。The rubbing peeling test by the organic solvent was carried out by rubbing the surface of the film of the ion-permeable compound with a solvent for impregnating the organic solvent of the electrolytic solution with a weight of 100 g, and observing whether or not the film was peeled off.
離子透過性化合物之較佳例係可舉例如多糖類、或使多糖類交聯者。Preferred examples of the ion-permeable compound include, for example, polysaccharides or cross-linkers of polysaccharides.
多糖類係單糖類(含有碳糖類之取代體及衍生物)，藉配糖體鍵而多數聚合之高分子化合物。藉水解而產生多數之單糖類者。一般稱10以上之單糖類聚合者為多糖類。多糖類係亦可具有取代基，可舉例如醇性羥基以胺基所取代之多糖類(胺基糖)、以羧基或烷基所取代者、使多糖類去乙醯化者等。多糖類亦可為均多糖、雜多糖者之任一者。A polysaccharide-based monosaccharide (a substituent and a derivative containing a carbon saccharide) is a polymer compound which is mostly polymerized by a saccharide bond. A person who produces a majority of monosaccharides by hydrolysis. Generally, a monosaccharide polymerizer of 10 or more is a polysaccharide. The polysaccharide may have a substituent, and examples thereof include a polysaccharide (amino sugar) in which an alcoholic hydroxyl group is substituted with an amine group, a group in which a carboxyl group or an alkyl group is substituted, and a polysaccharide in which the polysaccharide is deacetylated. The polysaccharide may be any of a homopolysaccharide or a heteropolysaccharide.
多糖類之具體例可舉例如瓊脂糖、直鏈澱粉、支鏈澱粉、***聚糖、***糖、阿拉卡必()葡聚糖、藻酸、菊粉、角叉菜(Carrageenan)、半乳聚糖、半乳糖胺(chondrosamine)、葡聚糖、木聚糖、二甲木聚糖、羧基烷基幾丁質、幾丁質、糖原、葡糖甘露聚糖、硫酸角質素、聚唾液酸(Colominic acid)、軟骨素硫酸A、軟骨素硫酸B、軟骨素硫酸C、纖維素、葡聚糖、澱粉、透明質酸、多聚果糖、果膠酸、果膠質、乙醯肝素(Heparan)酸、肝素、半纖維素、戊聚糖、β－1,4’－甘露聚糖、α－1,6’－甘露聚糖、地衣澱粉、左聚糖、香菇多醣(Lentinan)、甲殼素等。此等之中宜為幾丁質、甲殼素。Specific examples of the polysaccharides include agarose, amylose, amylopectin, arabinan, arabinose, and arabica ( Glucan, alginic acid, inulin, carrageenan, galactan, chondrosamine, dextran, xylan, xylan, carboxyalkyl chitin , chitin, glycogen, glucomannan, keratan sulfate, colic acid, chondroitin sulfate A, chondroitin sulfate B, chondroitin sulfate C, cellulose, dextran, starch, Hyaluronic acid, polyfructose, pectic acid, pectin, Heparan acid, heparin, hemicellulose, pentosan, β-1,4'-mannan, α-1,6' - Mannan, Lichen, Levan, Lentinan, Chitin, and the like. Among these, chitin and chitin should be used.
用以使多糖類交聯之交聯劑，適宜為丙烯醯胺、丙烯腈、甲殼素吡咯烷酮羧酸鹽、羥基丙基甲殼素、酞酸酐、馬來酸酐、偏苯三甲酸酐、均苯四甲酸酐、酸酐之任一者。The crosslinking agent for crosslinking the polysaccharide is preferably acrylamide, acrylonitrile, chitin pyrrolidone carboxylate, hydroxypropyl chitin, phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic acid Any of an acid anhydride and an acid anhydride.
離子透過性化合物更具體例係可舉例如纖維素之丙烯醯胺所產生的交聯聚合物、纖維素之甲殼素吡咯烷酮羧酸鹽所產生之交聯聚合物、使甲殼素、幾丁質等以交聯劑交聯者，使多糖類以丙烯酸系添加劑或酸酐交聯者等。離子透過性化合物係可一種單獨或組合2種以上而使用。More specific examples of the ion-permeable compound include a cross-linked polymer produced by acrylamide of cellulose, a cross-linked polymer produced by chitin pyrrolidone carboxylate of cellulose, chitin, chitin, and the like. The crosslinking agent is a crosslinking agent, and the polysaccharide is crosslinked by an acrylic additive or an acid anhydride. The ion-permeable compound may be used alone or in combination of two or more.
於皮膜a中所含有之離子透過性化合物與碳微粒子a的質量比(＝離子透過性化合物/碳微粒子a)宜為20/80~99/1，更宜為40/60~90/10。The mass ratio of the ion-permeable compound to the carbon fine particles a (= ion-permeable compound/carbon fine particle a) contained in the film a is preferably 20/80 to 99/1, more preferably 40/60 to 90/10.
皮膜a係依需要而亦可含有活性碳a。藉由活性碳a包含於皮膜a中，俾電雙層電容器之電容變高。又，所使用之活性碳a係可從後述之活性碳b所舉出者之中選擇。The film a may also contain activated carbon a as needed. Since the activated carbon a is contained in the film a, the capacitance of the tantalum double layer capacitor becomes high. Further, the activated carbon a used may be selected from those of the activated carbon b to be described later.
皮膜a係不受其形成方法而特別限定。例如，將使離子透過性化合物、碳微粒子a與依需要之活性碳a分散或溶解於溶劑而調製塗布劑，將此塗布劑塗布於導電性薄片，再乾燥而形成皮膜a。The film a is not particularly limited by the method of its formation. For example, a coating agent is prepared by dispersing or dissolving an ion-permeable compound, carbon fine particles a and an optional activated carbon a in a solvent, and applying the coating agent to a conductive sheet, followed by drying to form a film a.
塗布方法可舉例如澆鑄法、桿塗法、浸漬法、印刷法等。此等之方法中，就易控制皮膜之厚度而言，適宜為桿塗法、澆鑄法。The coating method may, for example, be a casting method, a rod coating method, a dipping method, a printing method, or the like. Among these methods, in terms of the thickness of the film to be easily controlled, a rod coating method or a casting method is suitable.
用於塗布劑之溶劑，只要為可使離子透過性化合物與碳微粒子a分散或溶解即可，並無特別限制。為調整塗布劑之黏度，宜使塗布劑之固形分率成為10質量%~100質量%之方式添加溶劑。又，溶劑係藉塗布後之乾燥而可除去約100%。The solvent used for the coating agent is not particularly limited as long as it can disperse or dissolve the ion-permeable compound and the carbon fine particles a. In order to adjust the viscosity of the coating agent, it is preferred to add a solvent so that the solid content of the coating agent is 10% by mass to 100% by mass. Further, the solvent can be removed by about 100% by drying after coating.
繼而，宜乾燥後，使皮膜a熱硬化。由多糖類或使多糖類交聯者等所構成之離子透過性化合物係包含以加熱硬化者。為使皮膜a以熱進一步硬化，可於塗布劑中添加前述之交聯劑。Then, after drying, the film a is thermally hardened. The ion-permeable compound composed of a polysaccharide or a polysaccharide-crosslinking person or the like contains a person who is cured by heat. In order to further harden the film a by heat, the aforementioned crosslinking agent may be added to the coating agent.
皮膜a之厚度較佳係0.01μm以上50μm以下，更宜為0.1μm以上10μm以下。若厚度太薄，有無法得到內部電阻之降低等所希望效果之傾向。若膜厚太厚，電雙層電容器之體積中的皮膜a占有之體積浪費地變大，電容器之每一體積的電容量易變低。The thickness of the film a is preferably 0.01 μm or more and 50 μm or less, more preferably 0.1 μm or more and 10 μm or less. If the thickness is too thin, there is a tendency that a desired effect such as a decrease in internal resistance cannot be obtained. If the film thickness is too thick, the volume occupied by the film a in the volume of the electric double layer capacitor is wastefully increased, and the capacitance of each volume of the capacitor tends to become low.
皮膜a係宜密接於導電性薄片，不被剝離者，具體上係宜在膠帶剝離試驗(JIS DO202－1988)中不剝離。The film a is preferably adhered to the conductive sheet and is not peeled off. Specifically, it is preferably not peeled off in the tape peeling test (JIS DO202-1988).
本發明之較佳的實施態樣中之電雙層電容器用電極，係具有前述電雙層電容器用集電體、與於該集電體之皮膜a上所具備的含有黏結劑、碳微粒子b及活性碳b之皮膜b。An electrode for an electric double layer capacitor according to a preferred embodiment of the present invention includes the current collector for an electric double layer capacitor and a binder containing carbon particles b on a film a of the current collector. And the film b of activated carbon b.
構成本發明之較佳的實施態樣中之電雙層電容器用電極的皮膜b係含有黏結劑、碳微粒子b及活性碳b者。The film b constituting the electrode for an electric double layer capacitor in the preferred embodiment of the present invention contains a binder, carbon particles b, and activated carbon b.
黏結劑係於電雙層電容器用電極所使用之公知的黏結劑。黏結劑係可舉例如聚偏氟乙烯、聚四氟乙烯、苯乙烯丁二烯橡膠等。此黏結劑溶解或分散於N－甲基吡咯烷酮、二甲苯、水等之溶劑，形成液狀者，適宜於與後述之活性碳b等的混合。又，皮膜b中亦可含有前述之離子透過性化合物。The binder is a well-known binder used for electrodes for electric double layer capacitors. The binder may, for example, be polyvinylidene fluoride, polytetrafluoroethylene or styrene butadiene rubber. The binder is dissolved or dispersed in a solvent such as N-methylpyrrolidone, xylene or water to form a liquid, and is suitable for mixing with activated carbon b or the like described later. Further, the film b may contain the above-described ion permeable compound.
活性碳b係就提高電容量之觀點，宜為比表面積大者。具體上，活性碳b宜BET比表面積為800~2500m2 /g者。活性碳b係宜平均粒徑(D50)為1μm~50μm者。此處，以活性碳b之平均粒徑(D50)藉微追縱粒度分布計所測定之50%累積粒子徑(μm)。The activated carbon b system is preferably a large specific surface area from the viewpoint of increasing the capacitance. Specifically, the activated carbon b preferably has a BET specific surface area of 800 to 2500 m 2 /g. The activated carbon b is preferably one having an average particle diameter (D50) of from 1 μm to 50 μm. Here, the 50% cumulative particle diameter (μm) measured by the micro-surrounding particle size distribution meter is the average particle diameter (D50) of the activated carbon b.
活性碳b係可採用自公知者。可舉例如椰子殼活性碳、纖維狀活性碳等。活性碳係亦可不受其賦予活性方法而特別限定，而亦可採用以水蒸氣賦予活性法、藥品賦予活性法等所得到者。又，為得到高電容之電容器，係適宜為鹼賦予活性處理者(鹼賦予活性碳)。鹼賦予活性碳可藉由例如使椰子殼、煤焦、聚合物碳化物、難石墨化性碳化物、易石墨化性碳化物在鹼金屬化合物之存在下進行熱處理所得到者。易石墨化性碳化物可使用例如石油系瀝青、煤系瀝青、及其等之有機溶劑可溶成分等的瀝青進行熱處理所得到者、或聚氯化乙烯系化合物的碳化物。鹼金屬化合物可舉例如氫氧化鈉、氫氧化鉀、碳酸鉀等。Activated carbon b can be used from known sources. For example, coconut shell activated carbon, fibrous activated carbon, or the like can be mentioned. The activated carbon system is not particularly limited as long as it is not subjected to the active method, and may be obtained by a steam-providing activity method, a drug-administering activity method, or the like. Further, in order to obtain a capacitor having a high capacitance, it is preferable to impart an alkali to an active processor (base-providing activated carbon). The base-derived activated carbon can be obtained, for example, by heat-treating a coconut shell, coal char, a polymer carbide, a non-graphitizable carbide, and an easily graphitizable carbide in the presence of an alkali metal compound. The easily graphitizable carbide can be obtained by heat-treating a pitch such as petroleum-based pitch, coal-based pitch, or an organic solvent-soluble component thereof, or a carbide of a polyvinyl chloride-based compound. The alkali metal compound may, for example, be sodium hydroxide, potassium hydroxide or potassium carbonate.
用於本發明之活性碳b係宜固化總體密度(Tap密度)在於0.3g/cm3 ~0.9g/cm3 之範圍內。若固化總體密度太小，充填密度變小，電雙層電容器之每一體積或每一格室之電容量成為降低傾向。若固化總體密度太大，每一重量之電容量降低，可保持電解液之量變成減少傾向，有時電容保持率會降低。The activated carbon b used in the present invention preferably has a cured overall density (Tap density) in the range of 0.3 g/cm 3 to 0.9 g/cm 3 . If the solidified overall density is too small, the packing density becomes small, and the capacitance of each volume or compartment of the electric double layer capacitor tends to decrease. If the overall density of the solidification is too large, the electric capacity per weight is lowered, and the amount of the electrolyte is kept to decrease, and the capacity retention rate is sometimes lowered.
皮膜b中之黏結劑與活性碳b之質量比(黏結劑/活性碳b)宜為50/50~1/99，更宜為30/70~3/97、碳微粒子b係可使用與作為上述碳微粒子a所例示者相同者，具體上係可使用乙炔黑、Kechen黑、氣相法碳纖維、石墨(黑鉛)等。碳微粒子b係宜於皮膜b中含有2~10質量%之範圍。The mass ratio of the binder to the activated carbon b in the film b (adhesive/activated carbon b) is preferably 50/50 to 1/99, more preferably 30/70 to 3/97, and the carbon microparticles b can be used and The carbon microparticles a are the same as those exemplified, and specifically, acetylene black, Kechen black, fumed carbon fiber, graphite (black lead) or the like can be used. The carbon fine particles b are preferably contained in the film b in a range of 2 to 10% by mass.
皮膜b之厚度係可依所希望之電容量而適當調整，但，較佳係10μm以上500μm以下、皮膜b係不受其形成方法而特別限定。例如，將使黏結劑、碳微粒子b與活性碳b分散或溶解於溶劑而調製塗布劑，將此塗布劑塗布於皮膜a之上，再乾燥而形成皮膜b。The thickness of the film b can be appropriately adjusted depending on the desired electric capacity. However, it is preferably 10 μm or more and 500 μm or less, and the film b is not particularly limited by the method for forming the film b. For example, a coating agent is prepared by dispersing or dissolving a binder, carbon fine particles b, and activated carbon b in a solvent, and applying the coating agent onto the film a, followed by drying to form a film b.
塗布方法可舉例如澆鑄法、桿塗法、浸漬法、印刷法等，但，無特別限定而可採用公知之方法。此等之方法中，就易控制皮膜之厚度而言，適宜為桿塗法、澆鑄法、用於塗布劑之溶劑，只要為可使活性碳b及碳微粒子b分散或溶解即可，並無特別限制。為調整塗布劑之黏度，宜於塗布劑中適量添加溶劑。又，溶劑係藉塗布後之乾燥及熱處理而可除去約100%。The coating method may, for example, be a casting method, a rod coating method, a dipping method, a printing method, or the like. However, a known method can be employed without particular limitation. In the above methods, the thickness of the coating film is preferably a rod coating method, a casting method, or a solvent for a coating agent, as long as the activated carbon b and the carbon microparticles b can be dispersed or dissolved. Special restrictions. In order to adjust the viscosity of the coating agent, it is preferred to add an appropriate amount of the solvent to the coating agent. Further, the solvent can be removed by about 100% by drying and heat treatment after coating.
本發明之較佳的實施態樣中之電雙層電容器係具備前述電雙層電容器用電極，可與該電極聚合之分隔膜、與浸漬前述電極及分隔膜之電解液。An electric double layer capacitor according to a preferred embodiment of the present invention includes the electrode for an electric double layer capacitor, a separator film which can be polymerized with the electrode, and an electrolyte solution which immerses the electrode and the separator.
電雙層電容器之電解液係可使用公知之非水溶劑電解質溶液、水溶性電解質溶液之任一者，進一步其他之電解液之外，亦可使用非水系電解質之高分子固體電解質及高分子凝膠電解質、離子性液體。The electrolytic solution of the electric double layer capacitor can be any one of a known nonaqueous solvent electrolyte solution and a water-soluble electrolyte solution, and further, other electrolytes, a polymer solid electrolyte of non-aqueous electrolyte and a polymer gel can be used. Glue electrolyte, ionic liquid.
水系(水溶性電解質溶液)者可舉例如硫酸水溶液、硫酸鈉水溶液、氫氧化鈉水溶液等。Examples of the water system (water-soluble electrolyte solution) include a sulfuric acid aqueous solution, a sodium sulfate aqueous solution, and an aqueous sodium hydroxide solution.
又，非水系(非水溶劑電解質溶液)者係使用以R1 R2 R3 R4 N＋ 或R1 R2 R3 R4 P＋ 所示之陽離子(R1 、R2 、R3 、R4 分別獨立地為碳數1~10的烷基或烯丙基)、與BF4 － 、PF6 － 、ClO4 － 等之陰離子所構成之4級銨鹽或4級磷鎓鹽作為電解質，使用碳酸乙烯酯、碳酸丙烯酯等之碳酸酯系非水溶劑作為溶劑者。又，電解質或溶劑亦可分別組合二種類以上而使用。Further, in the nonaqueous (nonaqueous solvent electrolyte solution), cations represented by R 1 R 2 R 3 R 4 N + or R 1 R 2 R 3 R 4 P + (R 1 , R 2 , R 3 , R 4 is independently an alkyl group having 1 to 10 carbon atoms or an allyl group, and a 4th-order ammonium salt or a 4-stage phosphonium salt composed of an anion of BF 4 - , PF 6 - , ClO 4 - or the like as an electrolyte A carbonate-based nonaqueous solvent such as ethylene carbonate or propylene carbonate is used as a solvent. Further, the electrolyte or the solvent may be used in combination of two or more types.
與電極重疊之分隔膜係只要為透過離子之多孔質分隔膜即可，較佳係可使用例如微孔性聚乙烯膜、微孔性聚丙烯膜、乙烯不織布、聚丙烯不織布、玻璃纖維混抄不織布等。The separator film to be overlapped with the electrode may be a porous separator film that transmits ions. For example, a microporous polyethylene film, a microporous polypropylene film, an ethylene nonwoven fabric, a polypropylene nonwoven fabric, a glass fiber mixed nonwoven fabric, or the like can be preferably used.
本發明之電雙層電容器係於一對之薄片狀電極之間介入分隔膜而與電解液同時地收藏於金屬殼體之銅幣型、使一對電極介由分隔膜捲繞而構成之捲繞型、複數重疊分隔膜與電極之層合型等的任一者之構成。The electric double layer capacitor of the present invention is a copper coin type in which a separator film is interposed between a pair of sheet-like electrodes and is housed in a metal case simultaneously with an electrolytic solution, and a pair of electrodes are wound by a separator film. The configuration of any one of the type and the plural overlapping separator film and the electrode laminate type.
本發明之較佳的實施態樣中之電雙層電容器係係可適用於電源系統。又，本發明之電雙層電容器係可適用於汽車、火車等之車輛用電源系統；船舶用電源系統；飛機用電源系統；攜帶電話、攜帶資訊終端、攜帶電子計算機等之攜帶電子機器用電源系統；事務機用電源系統；太陽電池電源系統；風力發電系統、燃料電池系統等之發電系統用電源系統；；通訊機器、電子標籤等。The electric double layer capacitor system in the preferred embodiment of the present invention is applicable to a power supply system. Moreover, the electric double layer capacitor of the present invention can be applied to a power supply system for a vehicle such as an automobile or a train; a power supply system for a ship; a power supply system for an aircraft; a power supply for a portable electronic device such as a mobile phone, a portable information terminal, and a portable electronic computer; System; power supply system for business machine; solar battery power system; power system for power generation system such as wind power generation system and fuel cell system; communication equipment, electronic label, etc.
以下，舉出實施例及比較例而具體地說明本發明，但本發明不限定於下述實施例。Hereinafter, the present invention will be specifically described by way of examples and comparative examples, but the present invention is not limited to the following examples.
準備由厚30μm之A1085材所構成的鋁箔。An aluminum foil composed of a 1010 m thick A1085 material was prepared.
準備使多糖類之甲殼素以均苯四甲酸酐交聯者作為離子透過性化合物。此離子透過性化合物之數目平均分子量係藉凝膠滲透色層分析(GPC)之測定為35000。又，此離子透過性化合物之離子透過度為2.05×10-2 S/cm(σ0 =4.54×10-6 S/cm、σ1 =33.5×10-6 S/cm、膜厚d=71μm)。It is prepared to use a chitin of a polysaccharide as a ion-permeable compound by crosslinking with pyromellitic anhydride. The number average molecular weight of the ion-permeable compound was determined by gel permeation chromatography (GPC) to be 35,000. Further, the ion permeability of the ion-permeable compound was 2.05 × 10 -2 S/cm (σ 0 = 4.54 × 10 -6 S/cm, σ 1 = 33.5 × 10 -6 S/cm, and film thickness d = 71 μm). ).
使此離子透過性化合物與碳微粒子a(乙炔黑：平均粒子徑40nm)與水就質量比率以40：40：20混合，混練而得到糊劑。The ion-permeable compound and carbon fine particles a (acetylene black: average particle diameter: 40 nm) were mixed with water at a mass ratio of 40:40:20, and kneaded to obtain a paste.
使用薄層塗布器(間隙：10μm)，而藉澆鑄法於鋁箔塗布前述之糊劑，然後在180℃之空氣中乾燥3分鐘，於鋁箔上形成一含有離子透過性化合物與碳微粒子a的皮膜a，得到電雙層電容器用集電體。Using a thin layer coater (gap: 10 μm), the paste was applied to the aluminum foil by casting, and then dried in air at 180 ° C for 3 minutes to form a film containing an ion permeable compound and carbon particles a on the aluminum foil. a, a current collector for an electric double layer capacitor is obtained.
乾燥後之皮膜a之厚度為5μm，皮膜a中之碳微粒子a的含有率為60質量%。以一般之測試機測定電傳導度後，可確認出有充分的通電。The thickness of the film a after drying was 5 μm, and the content of the carbon fine particles a in the film a was 60% by mass. After measuring the electrical conductivity by a general tester, it was confirmed that sufficient energization was obtained.
圖1係概念地表示上述所得到之集電體的截面構造圖。如圖1所示般，本發明之電雙層電容器用集電體係於鋁箔(1)之上層合皮膜a(2)。於皮膜a(2)中係包含碳微粒子(3)與離子透過性化合物(4)。Fig. 1 conceptually shows a cross-sectional structural view of the current collector obtained as described above. As shown in Fig. 1, the current collecting system for an electric double layer capacitor of the present invention laminates the film a (2) on the aluminum foil (1). The carbon film (3) and the ion-permeable compound (4) are contained in the film a (2).
於實施例1所得到之集電體上，塗布由下述處方之活性碳、碳微粒子b、黏結劑及溶劑所構成的糊劑，形成以厚度200μm之活性碳作為主成分的分極性電極層(皮膜b)，製成電雙層電容器用電極。On the current collector obtained in Example 1, a paste composed of activated carbon, carbon fine particles b, a binder, and a solvent prescribed below was applied to form a polar electrode layer having activated carbon having a thickness of 200 μm as a main component. (film b), an electrode for an electric double layer capacitor.
活性碳：比表面積1500m2 /g之鹼賦予活性活性碳 85質量份碳微粒子b：乙炔黑(平均粒子徑40nm) 5質量份黏結劑：聚偏氟乙烯(PVDF) 10質量份溶劑：N－甲基－2－吡咯烷酮(NMP) 8.5質量份(活性碳的10質量%)Activated carbon: base having a specific surface area of 1500 m 2 /g to give active activated carbon 85 parts by mass of carbon fine particles b: acetylene black (average particle diameter: 40 nm) 5 parts by mass of binder: polyvinylidene fluoride (PVDF) 10 parts by mass of solvent: N- Methyl-2-pyrrolidone (NMP) 8.5 parts by mass (10% by mass of activated carbon)
其次，使電雙層電容器用電極符合評估用電容器的大小，而以直徑20mm沖出2片。使分隔膜挾於其間而重疊2片之電極，收容於評估用電容器容器中，使有機電解液注入於該容器中，浸漬電極等，最後蓋住容器，而製成評估用電雙層電容器。Secondly, the electrode for the electric double layer capacitor is made to conform to the size of the evaluation capacitor, and the diameter is 20 mm. Rush out 2 pieces. The electrode in which the separator film was sandwiched between the two sheets was placed in the capacitor container for evaluation, the organic electrolyte solution was injected into the container, the electrode or the like was immersed, and the container was finally covered to prepare an electric double layer capacitor for evaluation.
有機電解液係使用溶劑為碳酸丙烯酯、電解質為(C2 H5 )4 NBF4 之富山藥品工業(股)製之商品名LIPASTE－P/EAFIN(1莫耳/升)。The organic electrolytic solution is a product name LIPASTE-P/EAFIN (1 mol/liter) manufactured by Toyama Pharmaceutical Industries Co., Ltd., in which the solvent is propylene carbonate and the electrolyte is (C 2 H 5 ) 4 NBF 4 .
圖2係概念地表示上述所得到之電極的截面構造圖、如圖2所示般，本發明之電雙層電容器用電極係於鋁箔(1)之上層合皮膜a(2)，於其皮膜a之上進一步層合皮膜b(6)。於皮膜b(6)中係含有黏結劑(7)、活性碳(5)、及碳微粒子b(3)。2 is a cross-sectional structural view conceptually showing the electrode obtained as described above. As shown in FIG. 2, the electrode for an electric double layer capacitor of the present invention is laminated on the aluminum foil (1) to laminate the film a(2) on the film. The film b (6) is further laminated on a. The film b (6) contains a binder (7), activated carbon (5), and carbon fine particles b (3).
測定上述所得到之電雙層電容器的阻抗及電容量、結果表示於表1中。The impedance and capacitance of the electric double layer capacitor obtained above were measured, and the results are shown in Table 1.
阻抗之測定係使用KIKUSUI公司製的阻抗測定器(PAN110－5AM)，以1KHz之條件實施。電容量之測定係使用北斗電工(股)製充放電試驗製置(HJ－101SM6)，以電流密度1.59mA/cm2 以0~2.5V進行充放電。從第2次之定電流放電時所測定之放電曲線算出每一電雙層電容器的格室之電容量(F/格室)。電容保持率(%)係以(第20次之電容量)/(第2次之電容量)×100而算出。The impedance was measured using a impedance measuring instrument (PAN110-5AM) manufactured by KIKUSUI Co., Ltd. at 1 kHz. The capacitance was measured by a charge and discharge test (HJ-101SM6) manufactured by Hokuto Electric Co., Ltd., and charged and discharged at a current density of 1.59 mA/cm 2 at 0 to 2.5 V. The capacitance (F/cell) of the cell of each electric double layer capacitor was calculated from the discharge curve measured at the second constant current discharge. The capacitance retention ratio (%) was calculated by (20th power capacity) / (2nd power capacity) × 100.
從表1可知，使用本發明之集電體所得到的電雙層電容器係阻抗低、每一格室之電容量高、電容保持率亦良好。As is clear from Table 1, the electric double layer capacitor obtained by using the current collector of the present invention has low impedance, high capacitance per cell, and good capacitance retention.
使在實施例1所使用之碳微粒子a(乙炔黑)更換成氣相法碳纖維(VGCF(註冊商標)昭和電工公司製、纖維長20μm)外，其餘係與實施例1同樣做法而得到電雙層電容器用集電體。使用此集電體外，其餘係與實施例2相同做法而得到電雙層電容器用電極、及電雙層電容器。將評估結果表示於表1中。The carbon microparticles a (acetylene black) used in Example 1 were replaced with a gas phase carbon fiber (VGCF (registered trademark), manufactured by Showa Denko Co., Ltd., fiber length: 20 μm), and the same procedure as in Example 1 was carried out to obtain an electric double. A collector for a layer capacitor. Using this current collector, the electrode of the electric double layer capacitor and the electric double layer capacitor were obtained in the same manner as in the second embodiment. The evaluation results are shown in Table 1.
使在實施例2所使用之碳微粒子b(乙炔黑)更換成氣相法碳纖維(VGCF昭和電工公司製、纖維長20μm)外，其餘係與實施例2同樣做法而得到電雙層電容器用電極及電雙層電容器。將評估結果表示於表1中。An electrode for an electric double layer capacitor was obtained in the same manner as in Example 2 except that the carbon microparticles b (acetylene black) used in Example 2 were replaced with a vapor-phase carbon fiber (manufactured by VGCF, Showa Denko Co., Ltd., fiber length: 20 μm). And electric double layer capacitors. The evaluation results are shown in Table 1.
準備使多糖類之幾丁質以馬來酸酐交聯者作為離子透過性化合物。此數目平均分子量係藉GPC測定為30000。使用此而與實施例1同樣做法而製成糊劑，得到由含有離子透過性化合物及碳微粒子之皮膜、與鋁箔所構成之集電體。It is prepared to use a chitin of a polysaccharide as a ion-permeable compound by crosslinking with maleic anhydride. This number average molecular weight was determined to be 30,000 by GPC. Using this, a paste was prepared in the same manner as in Example 1 to obtain a current collector comprising a film containing an ion-permeable compound and carbon fine particles and an aluminum foil.
繼而藉由使用此集電體而與實施例2同樣的步驟，得到電雙層電容器。同樣地測定電容量、電容保持率、內部電阻、阻抗，將結果表示於表1中。Then, an electric double layer capacitor was obtained by the same procedure as in Example 2 by using this current collector. The capacitance, the capacitance retention ratio, the internal resistance, and the impedance were measured in the same manner, and the results are shown in Table 1.
在實施例1中，除將鋁箔之材料從A1085材變更成A3003材，使離子透過性化合物變更成以丙烯腈使多糖類之甲殼素交聯者(數目平均分子量係藉GPC測定為31000)以外，其餘係與實施例1相同做法而製成糊劑，得到由含離子透過性化合物及碳微粒子之皮膜、與鋁箔所構成之集電體。In the first embodiment, except that the material of the aluminum foil was changed from the A1085 material to the A3003 material, and the ion-permeable compound was changed to the chitin cross-linking of the polysaccharide with acrylonitrile (the number average molecular weight was 31,000 as measured by GPC). In the same manner as in Example 1, a paste was prepared to obtain a current collector composed of an ion-permeable compound and a film of carbon fine particles and an aluminum foil.
繼而藉由使用此集電體而與實施例2同樣的步驟，得到電雙層電容器。同樣地測定電容量、電容保持率、內部電阻、阻抗，將結果表示於表1中。Then, an electric double layer capacitor was obtained by the same procedure as in Example 2 by using this current collector. The capacitance, the capacitance retention ratio, the internal resistance, and the impedance were measured in the same manner, and the results are shown in Table 1.
在實施例1中，除將離子透過性化合物變更成以偏苯三甲酸酐使多糖類之甲殼素交聯者(此數目平均分子量係藉GPC測定為22000)以外，其餘係與實施例1相同做法而製成糊劑，得到由含離子透過性化合物及碳微粒子之皮膜、與鋁箔所構成之集電體。In Example 1, except that the ion-permeable compound was changed to cross-link the chitin of the polysaccharide with trimellitic anhydride (the number average molecular weight was 22,000 as measured by GPC), the same procedure as in Example 1 was carried out. Further, a paste was prepared to obtain a current collector composed of an ion-permeable compound and a film of carbon fine particles and an aluminum foil.
繼而藉由使用此集電體而與實施例2同樣的步驟，得到電雙層電容器。同樣地測定電容量、電容保持率、內部電阻、阻抗，將結果表示於表2中。Then, an electric double layer capacitor was obtained by the same procedure as in Example 2 by using this current collector. The capacitance, the capacitance retention ratio, the internal resistance, and the impedance were measured in the same manner, and the results are shown in Table 2.
準備使多糖類之甲殼素以丙烯腈交聯者作為離子透過性化合物。使此化合物形成0.5μm之厚而成膜以進行膠帶剝離試驗。於全部100片看不出剝離。又，此化合物之數目平均分子量係藉GPC測定為26000。It is prepared to use a chitin of a polysaccharide as an ion-permeable compound by crosslinking with acrylonitrile. This compound was formed into a film having a thickness of 0.5 μm to carry out a tape peeling test. No peeling was observed in all 100 sheets. Further, the number average molecular weight of this compound was 26,000 as determined by GPC.
除使此甲殼素以丙烯腈交聯者、與使甲殼素以偏苯三羧酸酐交聯者(數目平均分子量係藉GPC測定為22000)合併使用以外，其餘係與實施例1相同做法而製成糊劑，得到由含離子透過性化合物及碳微粒子之皮膜、與鋁箔所構成之集電體。The same procedure as in Example 1 was carried out except that the chitin was crosslinked with acrylonitrile and the chitin was crosslinked with trimellitic anhydride (the number average molecular weight was 22,000 as measured by GPC). As a paste, a current collector composed of an ion-permeable compound and a film of carbon fine particles and an aluminum foil was obtained.
繼而藉由與實施例2同樣的步驟，得到電雙層電容器。同樣地測定電容量、電容保持率、內部電阻、阻抗，將結果表示於表2中。Then, an electric double layer capacitor was obtained by the same procedure as in the second embodiment. The capacitance, the capacitance retention ratio, the internal resistance, and the impedance were measured in the same manner, and the results are shown in Table 2.
除不使用碳微粒子a亦即更換成於實施例1使用之糊劑而使用只含有離子透過性化合物及水之液體以外，其餘係與實施例1相同，而得到電雙層電容器用集電體。評估結果表示於表2中。以一般之測試機測定電傳導度，但電流不流通。The current collector of the electric double layer capacitor was obtained in the same manner as in Example 1 except that the carbon microparticles a were used instead of the paste used in Example 1, and the liquid containing only the ion permeable compound and water was used. . The results of the evaluation are shown in Table 2. The electrical conductivity was measured by a general tester, but the current did not flow.
除將實施例2中所使用之集電體變更成由表面被蝕刻處理之A1085材所構成之鋁箔以外，其餘係與實施例2相同做法而得到電雙層電容器集電體、及電雙層電容器。將結果表示於表2中。An electric double layer capacitor current collector and an electric double layer were obtained in the same manner as in Example 2 except that the current collector used in Example 2 was changed to an aluminum foil composed of A1085 material whose surface was etched. Capacitor. The results are shown in Table 2.
除將離子透過性化合物更換成PVDF以外，其餘係與實施例1及實施例2同樣做法而製成電雙層電容器。PVDF之離子透過度為0.81×10-2 S/cm(σ0 =4.54×10-6 S/cm、σ1 =6.42×10-6 S/cm、膜厚d=433μm)。使電容保持率、內部電阻以與實施例2相同的條件進行測定。結果表示於表2中。可製造電雙層電容器，但，若以浸漬碳酸丙烯酯之布摩擦集電體表面，則產生很大剝離。認為於比較例3所得到之電雙層電容器係初期特性即使良好，亦無法承受長期間的使用。An electric double layer capacitor was produced in the same manner as in the first embodiment and the second embodiment except that the ion permeable compound was replaced with PVDF. The ion permeability of PVDF was 0.81 × 10 -2 S/cm (σ 0 = 4.54 × 10 -6 S/cm, σ 1 = 6.42 × 10 -6 S/cm, and film thickness d = 433 μm). The capacity retention and internal resistance were measured under the same conditions as in Example 2. The results are shown in Table 2. An electric double layer capacitor can be manufactured. However, if the surface of the current collector is rubbed with a cloth impregnated with propylene carbonate, a large peeling occurs. It is considered that even if the initial characteristics of the electric double layer capacitor obtained in Comparative Example 3 are good, it cannot be used for a long period of time.
除將離子透過性化合物更換成PVA(聚乙烯醇)黏結劑以外，其餘係與實施例1及實施例2同樣做法而製成電雙層電容器。使電容保持率、內部電阻以與實施例2相同的條件進行測定。結果表示於表2中。可製造電雙層電容器，但，於集電體之階段，實施與比較例3相同之膠帶剝離試驗後集電體表面產生很大剝離。於比較例4所得到之電雙層電容器係初期之特性即使良好，亦無法承受長期間的使用。An electric double layer capacitor was produced in the same manner as in Example 1 and Example 2 except that the ion permeable compound was replaced with a PVA (polyvinyl alcohol) binder. The capacity retention and internal resistance were measured under the same conditions as in Example 2. The results are shown in Table 2. An electric double layer capacitor can be produced. However, at the stage of the current collector, the same peeling test as in Comparative Example 3 was carried out, and the surface of the current collector was largely peeled off. The electric double layer capacitor obtained in Comparative Example 4 was not able to withstand long-term use even if it had good initial characteristics.
若依表1及表2可知，相較於比較例，使用本發明之電雙層電容器用集電體的電雙層電容器(實施例)，任一者均阻抗低，電容量很大，電容保持率亦優。亦即，結論為可以大電流進行充放電(急速充放電)，較習知之電雙層電容器更高性能。As can be seen from Tables 1 and 2, the electric double layer capacitor (Example) using the current collector for an electric double layer capacitor of the present invention has a low impedance and a large capacitance, compared with the comparative example. The retention rate is also excellent. That is, the conclusion is that charging and discharging (quick charging and discharging) can be performed at a large current, which is higher in performance than the conventional electric double layer capacitor.
本發明之電雙層電容器為低阻抗且成為高電容量之詳細原理係未知，但皮膜a中之離子透過性化合物及導電性之碳微粒子a分別擔離子及電子之移動，可使分極性電極層(皮膜b)與導電性薄片(鋁層)之間的離子及電子的來往圓滑地進行。The detailed principle that the electric double layer capacitor of the present invention has low impedance and high capacitance is unknown, but the ion permeable compound in the film a and the conductive carbon particles a respectively carry the movement of ions and electrons, and the polar electrode can be used. The exchange of ions and electrons between the layer (film b) and the conductive sheet (aluminum layer) proceeds smoothly.
1．．．鋁箔1. . . Aluminum foil
2．．．皮膜a2. . . Film a
3．．．碳微粒子3. . . Carbon particles
4．．．離子導電性化合物4. . . Ionic conductive compound
5．．．活性碳b5. . . Activated carbon b
6．．．皮膜b(分極性電極層)6. . . Film b (polar electrode layer)
7．．．黏結劑7. . . Adhesive
圖1係表示實施例1所得到之電雙層電容器用集電體的截面構造之概念圖。Fig. 1 is a conceptual diagram showing a cross-sectional structure of a current collector for an electric double layer capacitor obtained in Example 1.
圖2係表示實施例2所得到之電雙層電容器用電極的截面構造之概念圖。Fig. 2 is a conceptual diagram showing a cross-sectional structure of an electrode for an electric double layer capacitor obtained in Example 2.
圖3係表示用以測定氟離子透過度所使用之玻璃格室圖。Fig. 3 is a view showing a glass cell used for measuring the transmittance of fluorine ions.
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