201209116 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種電極用黏合劑組成物。 •【先前技術】 如鋰離子蓄電池、鎳氫蓄電池等之蓄電池；鋰離子電 容器、電雙層電容器等之電容器之電化學裝置中，具備有 於集電體上形成電極活性物質層而成之層合體所構成之電 極。該電極中之電極活性物質層係將電極用漿料塗佈於集 電體上成爲塗膜，接著使該塗膜乾燥，較好使乾燥後之塗 膜經進一步壓製加工而形成。前述電極用漿料係藉由混合 電極用黏合劑組成物與電極活性物質而調製。前述電極用 黏合劑組成物爲例如使聚偏氟化乙烯等黏合劑成分溶解於 溶劑中而成之溶液或分散於分散介質中而成之分散體。 具備該種電極之電化學裝置中，電容、循環特性、放 電率特性等特性被認爲有問題。該等特性依據電極中所含 之電極活性物質及電解液之種類及量等，同時依據黏合劑 之特性而受到較大影響。例如，黏合劑之黏著特性不充分 ' 時，無法使足量之電極活性物質黏著於集電體上，或者電 * 極活性物質彼此之黏著力不足，結果所得電化學裝置之電 容變得不充分。又，有因重複充放電而使黏合劑黏著力降 低之情況。該情況下，重複充放電時，電極活性物質自集 電體上緩慢脫落，其結果成爲電化學裝置之電容經時降低 (循環特性不良）之問題。 -5- 201209116 據此，電化學裝置中使用之黏合劑要求電極活性物 質-集電體間之高的密著性以及電極活性物質相互間之高 黏著性，或即使因重複充放電，電極活性物質仍不會自集 電體脫落之高黏著持續性。 考慮到上述情況，而多數提案有標榜具備高的黏著性 與高的黏著持續性之黏合劑組成物》 例如，分別於特開2002-428 1 9號公報提案含有具有 源自含氟之（甲基）丙烯酸酯之構造單位之聚合物的黏合 劑組成物，而日本專利第3539448號說明書（特開平 8-2879 1 5號公報）中提案含有同時具有源自（甲基）丙 烯酸酯之構造單位、源自丙烯腈之構造單位、與源自不飽 和羧酸之構造單位之聚合物的黏合劑組成物，已達到某種 程度之成果。 近年來，電化學裝置開始搭載於汽車上，例如鋰離子 蓄電池等之蓄電池係作爲電動車及油電混合車之主電源而 使用，電雙層電容器等之電容器係作爲卡車等大型車之輔 助電源而使用。 汽車隨著使用區域·季節因素等，使用環境（尤其是 使用溫度）有顯著不同，因此汽車上搭載之電化學裝置要 求在較廣溫度範圍內安定地發揮性能。然而，已指出過去 習知之黏合劑組成物使用於汽車搭載用途時，因使用溫度 而產生各種問題。例如已指出使用上述特開2002-428 1 9 號公報之黏合劑組成物製造之電化學裝置，在低溫環境下 高速放電時放電率特性變差。使用上述日本專利第 -6 - 201209116 3 53 9448號說明書之黏合劑組成物製造之電化學裝置，在 高溫環境下之電化學安定性低，且放置於高溫環境下時有 自身放電之問題。 【發明內容】 本發明係基於以上情況而完成者。 本發明之目的係提供一種可獲得高黏著性，而且，賦 予低溫環境下之放電率特性，及高溫環境下之電化學安定 性二者均優異之電化學裝置之電極用黏合劑組成物。 若依據本發明，本發明之上述目的及優點可藉由以下 之電極用黏合劑組成物達成： 一種電極用黏合劑組成物，其含有具有源自以下述一 般式（1)表示之單體之構造單位（A)及源自α，β-不飽 和腈單體之構造單位（Β)之聚合物，且 前述構造單位（Α)之含有比例爲5〜60質量％， 前述構造單位（Β)之含有比例爲5〜40質量％，而 前述構造單位（Α)及前述構造單位（Β)之合計含 有比例爲10〜70質量％， R1201209116 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a binder composition for an electrode. • [Prior Art] A battery such as a lithium ion battery or a nickel-metal hydride battery; an electrochemical device of a capacitor such as a lithium ion capacitor or an electric double layer capacitor, which has a layer in which an electrode active material layer is formed on a current collector. The electrode formed by the combination. The electrode active material layer in the electrode is formed by applying a slurry for an electrode onto a current collector to form a coating film, and then drying the coating film, preferably by subjecting the dried coating film to further press working. The slurry for an electrode is prepared by mixing a binder composition for an electrode and an electrode active material. The electrode binder composition is, for example, a solution obtained by dissolving a binder component such as polyvinylidene fluoride in a solvent or a dispersion dispersed in a dispersion medium. In an electrochemical device having such an electrode, characteristics such as capacitance, cycle characteristics, and discharge rate characteristics are considered to be problematic. These characteristics are largely influenced by the type and amount of the electrode active material and the electrolyte contained in the electrode, and depending on the characteristics of the binder. For example, when the adhesive property of the adhesive is insufficient, a sufficient amount of the electrode active material cannot be adhered to the current collector, or the adhesion of the electroactive material to each other is insufficient, and as a result, the capacitance of the obtained electrochemical device becomes insufficient. . Further, there is a case where the adhesive adhesion is lowered by repeated charge and discharge. In this case, when the charge and discharge are repeated, the electrode active material gradually falls off from the current collector, and as a result, the capacitance of the electrochemical device decreases with time (the cycle characteristics are poor). -5- 201209116 Accordingly, the adhesive used in the electrochemical device requires high adhesion between the electrode active material and the current collector, and high adhesion between the electrode active materials, or electrode activity even by repeated charge and discharge. The substance still does not have the high adhesion persistence of the self-collecting body. In view of the above, most of the proposals have a binder composition that has high adhesion and high adhesion persistence. For example, the proposal in Japanese Patent Laid-Open Publication No. 2002-428 119 contains a fluorine-containing one. A binder composition of a polymer of a structural unit of acrylate, and a proposal for a structural unit derived from (meth) acrylate at the same time as disclosed in Japanese Patent No. 3539448 (Japanese Laid-Open Patent Publication No. Hei No. Hei No. Hei. A binder composition derived from a structural unit of acrylonitrile and a polymer derived from a structural unit of an unsaturated carboxylic acid has reached a certain degree of achievement. In recent years, electrochemical devices have been installed in automobiles, and batteries such as lithium ion batteries have been used as main power sources for electric vehicles and hybrid electric vehicles. Capacitors such as electric double-layer capacitors have been used as auxiliary power sources for large vehicles such as trucks. And use. Since the use environment (especially the use temperature) differs significantly depending on the use area and seasonal factors, the electrochemical device mounted on the vehicle is required to perform stably in a wide temperature range. However, it has been pointed out that the conventional binder composition is used in automobile-mounted applications, and various problems arise due to the use temperature. For example, an electrochemical device manufactured by using the adhesive composition of the above-mentioned JP-A-2002-428-19 has been shown, and the discharge rate characteristics are deteriorated at a high-speed discharge in a low-temperature environment. The electrochemical device manufactured by using the adhesive composition of the above-mentioned Japanese Patent No. -6 - 201209116 3 53 9448 has low electrochemical stability in a high temperature environment and has a problem of self-discharge when placed in a high temperature environment. SUMMARY OF THE INVENTION The present invention has been completed based on the above circumstances. SUMMARY OF THE INVENTION An object of the present invention is to provide an electrode binder composition for an electrochemical device which is excellent in both high-adhesiveness and discharge rate characteristics in a low-temperature environment and electrochemical stability in a high-temperature environment. According to the present invention, the above objects and advantages of the present invention can be attained by the following electrode binder composition: an electrode binder composition containing a monomer derived from the following general formula (1) a structural unit (A) and a polymer derived from a structural unit (Β) of an α,β-unsaturated nitrile monomer, and the content ratio of the above structural unit (Α) is 5 to 60% by mass, and the aforementioned structural unit (Β) The content ratio is 5 to 40% by mass, and the total content of the structural unit (Α) and the structural unit (Β) is 10 to 70% by mass, R1.
I -般式（1 )I - General (1)
Hz C = C IHz C = C I
C *= 0 I 0 — R: (但，R1表示氫原子或甲基，R2表示碳數1~18之氟化烴 201209116C *= 0 I 0 — R: (However, R1 represents a hydrogen atom or a methyl group, and R2 represents a hydrogen fluoride having a carbon number of 1 to 18 201209116
【實施方式】 以下針對本發明之電極用黏合劑組成物詳細加以說明 〈電極用黏合劑組成物〉 本發明之電極用黏合劑組成物含有具有源自以上述一 般式（I)表示之單體之構造單位（A)及源自α，β-不飽 和腈單體之構造單位（Β)之聚合物（以下稱爲「特定聚 合物」）。該電極用黏合劑組成物可進而含有液狀介質， 可含有任意增黏劑。本發明之電極用黏合劑組成物亦可進 而含有乳化劑、聚合起始劑或其殘渣、界面活性劑、中和 劑等其他成分。 [特定聚合物] 本發明之電極用黏合劑組成物中含有之特定聚合物具 有構造單位（Α)及構造單位（Β)。該特定聚合物除構 造單位（Α)及構造單位（Β)以外，亦可進而具有其他 構造單位。 (構造單位（A )) 本發明中之特定聚合物具有源自以上述一般式（1) 表示之單體之構造單位（A)。 -8- 201209116 上述一般式（1)中之R2可列舉爲例如碳數丨〜18之 氟化烷基 '碳數6〜18之氟化芳基、碳數7〜18之氟芳院 基等。R2較好爲碳數1〜11之氟化烷基，最好爲以下述― 般式（2 )表示之基。 Η ~C-R3 (2) R4 (但，R3表示氫原子或碳數1~1〇之氟化烴基，R4表示碳 數1〜1 〇之氟化烴基）。 上述一般式（2)中之R3及R4之碳數1〜10之氟化烴 基較好爲碳數1〜10之氟化烷基。 以上述一般式（2 )表示之基之較佳具體例列舉爲例 如2,2,2-三氟乙基、1，1,1-三氟丙_2·基、2-(全氟辛基） 乙基、2,2,3,3-四氟丙基、2,2,3,4,4,4-六氟丁基、 1H，1H，9H-全氟-卜壬基、1H，1H-11H-全氟十一烷基、全氟 辛基等，該等中更好爲2,2,2-三氟乙基及2,2,2-三氟異丙 基，最好爲2,2,2 -三氟乙基。 .上述一般式（2)中，較好R3爲氫原子，R4爲碳數 1~3之氣化院基。 導入構造單位（A)之以上述一般式（1)表不之單 體可僅單獨使用上述中之一種，亦可混合由上述選出之兩 種以上使用。 (構造單位（B )) -9- 201209116 本發明中之特定聚合物具有上述構造單位（A)，同 時具有源自α，/3-不飽和腈單體之構造單位（B)。 導入構造單位（Β)之〇:，/?-不飽和腈單體之具體例 可列舉爲例如（甲基）丙烯腈、α -氯丙烯腈、氰化亞乙 烯等。該等中，較好爲（甲基）丙烯腈等，更好爲丙烯腈 。該等α，/3-不飽和腈單體可單獨使用一種或可組合兩種 以上使用。 (其他構造單位之種類） 如上述，本發明中之特定聚合物除構造單位（Α)及 構造單位（Β )以外，亦可進而具有其他構造單位。該等 其他構造單位可列舉爲源自不飽和羧酸單體之構造單位（ C ) ' 式 般 - 述 下 以 自 源 D 位 單 造 構 之 澧 SH 單 之 示 表 出 選 組 群 成 組 所 澧 SB 單 基 烯 乙 族 香 芳 及 烯 二 軛 共 由 自 源 C 位 位單 單造 造構 構之 之體 體單 單他 limit 種其 一 自 少源 至 之 及 o R 5 II I RICICIO II C 2 贼 (但’ R5表示氫原子或甲基’ R6表示碳數之烴基） -10- 201209116 導入構造單位（C)之步飽和羧酸單體可列舉爲例如 不飽和單羧酸、不飽和二羧酸、不飽和二羧酸之單烷酯、 不飽和二羧酸之單醯胺等。 上述單羧酸可列舉爲例如（甲基）丙烯酸、巴豆酸等 ， • 上述不飽和二羧酸可列舉爲例如馬來酸、富馬酸、衣 康酸等。導入構造單位（C)之不飽和羧酸單體係如上述 ，較好爲（甲基）丙烯酸及衣康酸，最好爲甲基丙烯酸。 該等不飽和羧酸單體可單獨使用一種或組合兩種以上 使用。 上述一般式（3)中之R6較好爲碳數1〜12之烷基， 可列舉爲例如甲基、乙基、正丙基、異丙基、正丁基、異 丁基、正戊基、異戊基、正己基、2-乙基己基、正辛基、 異壬基、正癸基等。 導入構造單位（D)之以上述一般式（3)表示之單 體可單獨使用一種或組合兩種以上使用。 導入構造單位（E)之單體中，作爲共軛二烯可列舉 爲例如1,3-丁二烯、2-甲基- 〗，3-丁二基（異戊間二烯）、 . 2,3-二甲基-1,3-丁 二烯、2-氯-1，3-丁二烯（氯丁 二烯）等 » 至於芳香族乙烯基單體可列舉爲例如苯乙烯、α -甲 基苯乙烯、對-甲基苯乙烯、乙烯基甲苯、氯苯乙烯、二 乙烯基苯等。 導入構造單位（Ε)之單體可單獨使用一種或組合兩 -11 - 201209116 種以上使用。 導入構造單位（F )之其他單體可列舉爲例如（甲基 )丙烯酸羥基甲酯、（甲基）丙烯酸羥基乙酯等（甲基） 丙烯酸羥基烷酯； 乙二醇二（甲基）丙烯酸酯等多官能基（甲基）丙烯 酸酯單體； 乙酸乙烯酯、丙酸乙烯酯等羧酸乙烯酯； 不飽和二羧酸之酸酐； 甲醯 、 基 胺烷 醯基 烯胺 。 丙之上 基酸以 甲羧種 基和兩 甲飽或 基不種 胺性一 ;甲烯之 胺二乙出 醯、等選 單胺胺中 之醯醯等 酸烯烯該 羧丙丙由 二基基用 和乙甲使 飽基基可 不胺丙， 基等 胺 胺 (特定聚合物中之各構成單位之含有比例） 特定聚合物中之構造單位（A)之含有比例爲全部構 造單位中之5~60質量％，較好爲7~55質量％。構造單位 (A )之含有比例過小時，有所得電化學裝置之循環特性 降低之虞。另一方面，構造單位（A)之含有比例過大時 ，有難以形成對集電體之密著性高之電極活性物質層之情 況° 特定聚合物中之構造單位（B)之含有比例爲全部構 造單位中之5〜4 0質量％，較好爲5〜3 5質量％。構造單位 (B )之含有比例過小時，有所得電化學裝置在高溫環境 下儲存時之自身放電變大，成爲耐久性較低者之情況。另 -12 - 201209116 一方面，構造單位（B)之含有比例過大時，有所得電極 活性物質層變得堅硬而脆之傾向’，有成爲對集電體之密著 性或柔軟性較低者。 本發明中之特定聚合物中，上述構造單位（A)及上 述構造單位（B)之合計含有比例，爲全部構造單位中之 • 1〇〜70質量％，較好爲15〜65質量％。該比例在上述範圍 內時，可進一步提高低溫環境下之放電率特性及高溫環境 下之電化學安定性，故較佳》 本發明中之特定聚合物具有構造單位（A)及構造單 位（B )，以及構造單位（C )時，本發明之黏合劑組成 物與電極活性物質混合時電極活性物質不會凝聚，可製造 電極活性物質之分散性良好之電極用漿料，而較佳。相反 的，構造單位（C)之含有比例太多時特定聚合物之耐氧 化性變差，故因重複充放電使聚合物氧化劣化，而變得無 法保持電極活性物質層，其結果，有發生充放電特性經時 劣化之不利情況。考慮到該等情況，特定聚合物中之構造 單位（C )之含有比例，在全部構造單位中較好爲1 0質量 %以下，更好爲質量％。 ' 含有具有構造單位（A)及構造單位（B)以及構造 ' 單位（D)之特定聚合物之電極用黏合劑組成物使用於正 極或電容器之電極時，產生集電體與電極活性物質層間之 密著性提高之優點。相反的，構造單位（D )之含有比例 過多之特定聚合物，有其離子導電性及耐氧化性變差，其 結果，有發生電極電阻上升及充放電特性之經時劣化之缺 -13- 201209116 點之情況。考慮到該等，特定聚合物中之構造單位（D) 之含有比例在全部構造單位中較好爲90質量％以下，更 好爲25〜80質量％。 含有具有構造單位（A)及構造單位（B)以及構造 單位（E)之特定聚合物之電極用黏合劑組成物使用於負 極時，會產生對於一般使用作爲負極活性物質之碳材料（ 例如石墨等）具有適度黏著性之優點。而且，所得電極層 層爲柔軟性或成爲對集電體之密著性良好者。相反的，構 造單位（E)之含有比例過多時，特定聚合物之離子導電 性及耐氧化性變差，故發生電極電阻上升及充放電特性經 時劣化之缺點。考慮到該等，特定聚合物中之構造單位（ E)之含有比例在全部構造單位中較好爲75質量％以下， 更好爲40~60質量％。 特定聚合物中之構造單位（F)之含有比例在全部構 造單位中較好爲10質量％以下。藉由成爲該範圍之比例 ，可抑制導入構造單位（C) 、( D) 、（E)伴隨產生之 離子導電性之劣化或密著性之劣化。 正極或電容器之電極中使用本發明之電極用黏合劑組 成物時，該組成物中所含之特定聚合物具有構造單位（A )及構造單位（B)以及構造單位（C)及構造單位（D) ，且該等含有比例在全部構造單位中，較好爲如下： 構造單位（A) : 10~50質量％，最好爲15〜40質量 % 構造單位（B ) : 5~30質量％，最好爲10~30質量％ 201209116 構造單位（A)與構造單位（B)之合計：20〜60質量 %，最好爲25~50質量％ 構造單位（C) : 2〜5質量％ 構造單位（D) : 30〜75質量％，最好爲3 5〜60質量％ 使用於正極或電容器之電極之電極用黏合劑組成物中 所含之特定聚合物，較好爲使構造單位（E )及構造單位 (F)之含有比例，在全部構造單位中各成爲5質量％以 下，較好亦不含有構造單位（E)及構造單位（F)之任一 者。 本發明之電極用黏合劑組成物使用於負極中時，該組 成物中含有之特定聚合物較好具有構造單位（A)及構造 單位（B)以及構造單位（C)及構造單位（E)，該等含 有比例在全部構造單位中較好爲如下者： 構造單位（A) : 10〜50質量％，最好爲15〜40質量％ 構造單位（B) : 5〜30質量％，最好爲10~30質量％ 構造單位（A)與構造單位（B)之合計：20〜60質量 %，最好爲25〜50質量％ 構造單位（C) : 2〜5質量％ 構造單位（E) : 45〜55質量％ 使用於負極中之電極用黏合劑組成物中所含之特定聚 合物，較好爲使構造單位（D)及構造單位（F)之含有 比例，在全部構造單位中各成爲5質量％以下，較好亦不 含構造單位（D)及構造單位（F)之任一者。 -15- 201209116 [特定聚合物之製造方法] 特定聚合物可如上述說明般使各單體之混合物聚合而 製造。單體混合物之聚合方法並無特別限制，但較好使用 乳化聚合法。藉由乳化聚合法獲得特定聚合物時，可適宜 使用乳化劑、聚合起始劑、分子量調節劑等。 上述乳化劑可單獨使用一種或組合兩種以上之陰離子 性界面活性劑、非離子性界面活性劑、兩性界面活性劑等 使用。上述陰離子性界面活性劑之具體例可列舉爲例如高 級醇之硫酸酯、烷基苯磺酸鹽、脂肪族磺酸鹽、聚乙二醇 院基釀之硫酸醋等； 非離子性界面活性劑之具體例可列舉爲例如聚乙二醇 之烷基酯、聚乙二醇之烷基醚、聚乙二醇之烷基苯基醚等 。至於上述兩性界面活性劑，可使用陰離子部份爲羧酸鹽 、硫酸酯鹽、磺酸鹽或磷酸酯鹽，陽離子部份爲胺鹽、四 級銨鹽之鹽。該種兩性界面活性劑之具體例可列舉爲例如 月桂基甜菜鹼、硬脂基甜菜鹼等甜菜鹼類；月桂基- /3-苯 胺、月桂基二（胺基乙基）甘胺酸、辛基二（胺基乙基） 甘胺酸等胺基酸類之界面活性劑等。 該種乳化劑之使用比例相對於所用之單體之合計1 〇〇 質量份，較好爲〇.5~5質量份。 上述聚合起始劑之具體例可列舉爲例如過硫酸鈉、過 硫酸鉀、過硫酸銨等水溶性聚合起始劑； 過氧化苯甲醯、月桂基過氧化物、2,2’-偶氮雙異丁腈 等油溶性聚合起始劑； ⑧ -16- 201209116 與亞硫酸氫鈉等之還原劑組合而成之氧化還原系聚合 起始劑等。該等聚合起始劑可單獨使用一種或組合兩種以 上使用。 聚合起始劑之使用比例相對於使用之單體之合計1 00 質量份較好爲〇.3~3質量份。 上述分子量調節劑之具體例可列舉爲例如氯仿、四氯 化碳等鹵化烴； 正己基硫醇、正辛基硫醇、正十二烷基硫醇、第三-十二烷基硫醇、硫代乙醇酸等硫醇衍生物； 二硫化二甲基黃原酸、二硫化二異丙基黃原酸等黃原 酸衍生物； 異松油烯、甲基苯乙烯二聚物等其他分子量調節 劑。 分子量調節劑之使用比例相對於所用之單體之合計 1 〇〇質量份較好爲5質量份以下。 乳化聚合較好在適當水性介質中進行，最好在水中進 行。該水性介質中之單體合計含有比例可爲10~50重量％ ，較好爲20〜40重量％。 乳化聚合之條件並無特別限制，例如可在聚合溫度 40〜8 5 °C，聚合時間2~1 6小時下進行。 最佳之乳化聚合之方法如下。亦即， 在至少含有聚合起始劑之水性介質中， 藉由添加單體混合物之乳化液（以下稱爲「單體乳化 液」）開始乳化聚合’且視需要，在單體乳化液之添加結 -17- 201209116 束後繼續聚合之方法。 含有上述聚合起始劑之水性介質之溫度較好爲 4 0〜8 5 °C，更好爲60〜80°C。此時，爲了避免聚合起始劑在 升溫過程中之分解，較好在水性介質升溫至某程度後（例 如成爲40〜70°C後），於其中添加聚合起始劑，且在聚合 起始劑添加後未經過過長之時間後，開始單體乳化液之添 加。 含有聚合起始劑之水性介質可進而含有上述分子量調 節劑等之任意成分。單體乳化液可藉由將單體及乳化劑以 及視需要之其他任意成分投入於水性介質中，使之經充分 攪拌而調整》該乳化液中之單體之含有比例較好爲40〜80 重量％，更好爲50〜70重量％。 將單體乳化液添加於含有聚合起始劑之水性介質中較 好以使聚合起始劑在反應液中不會局部化、不會產生不均 勻聚合反應之方式緩慢進行。添加時間較好爲0.5〜6小時 ，更好爲1 ~ 4小時。 單體乳化液之添加結束後，較好再繼續聚合。該情況 下繼續聚合之溫度較好爲40~85°C，更好爲60〜80°C。繼 續聚合之時間較好爲〇.5~6小時，更好爲1~4小時。自單 體乳化液之添加開始計之合計聚合時間較好爲1〜1 2小時 ，更好爲3~8小時。 [特定聚合物之特性] 本發明之電極用黏合劑組成物中含有之特定聚合物之 -18- 201209116 玻璃轉移溫度（Tg)較好爲-45〜25°c。 特定聚合物之玻璃轉移溫度（Tg )可如下述般測定。 將分散有特定聚合物之乳膠約4g流入5cmx4cm之鐵氟龍 (註冊商標）盤中，在70 °C之.恆溫槽中乾燥24小時，成 爲膜厚約100 之薄膜。自所得薄膜切出約10mg之試 料，將其採集至鋁容器中並密封。接著，使用示差掃描熱 量測定裝置（NETZSCH-GerStebau GmbH製造，型式「 DSC204F1」），在空氣環境下以升溫速度20°C/min於 -80°C〜100°C之溫度區域進行示差掃描熱量測定，基於所得 DSC圖求得玻璃轉移溫度Tg。由DSC圖求得玻璃轉移溫 度（Tg)時，係依據JIS K7121所記載之中間點之玻璃轉 移溫度之求法進行。 (液狀介質） 本發明之電極用黏合劑組成物含有如上述之特定聚合 物以及液狀介質。至於該液狀介質可爲水性介質或非水性 介質。 本發明之電極用黏合劑組成物較好爲使上述之特定聚 合物分散於水性介質中而成之漿料狀或乳膠狀，或使特定 聚合物溶解於非水性介質中而成之溶液狀。 上述水性介質含有水。水性介質可含有水以外之少量 非水介質。該種非水介質可列舉爲例如醯胺化合物、烴、 醇、酮、酯、胺化合物、內酯、亞颯、砸化合物等，可使 用由該等選出之一種以上。該種非水介質之含有比例相對 -19 - 201209116 於水性介質之全部較好爲ι〇質量％以下，更好爲5質量 %以下，水性介質最好不含非水介質而僅由水構成者。 特定聚合物在水性介質中較好爲粒子狀。水性介質中 之特定聚合物之數平均粒徑較好爲50~190nm，更好爲 7 0〜185 nm。藉由使特定聚合物之數平均粒徑落在上述範 圍內，在形成電極活性物質層時之乾燥步驟中，不會產生 聚合物粒子之移行，據此獲得之電極活性物質層之組成成 爲均一者，其結果，在電極活性物質與聚合物粒子及集電 體之間獲得足夠數量之有效黏著點，故可獲得高的黏著性 而較佳。 特定聚合物之數平均粒徑可使用大塚電子（股）製造 之雷射粒徑解析系統「LPA-3 000S/3 100」，以水作爲分散 介質，利用動態光散射法測定，由流體力學之直徑，以數 平均値計算出。 另一方面’上述非水性介質只要是可溶解特定聚合物 者均可適當使用。非水性介質之具體例可列舉爲例如正辛 院、異辛院、壬院、癸垸、十氫萘、薇嫌（pinene)、氯 十二烷等脂肪族烴； 環戊烷、環己烷、環庚烷、甲基環戊烷等環狀脂肪族 烴； 氯苯、氯甲苯、乙基苯、二異丙基苯、枯烯等芳香族 烴； 甲醇、乙醇、丙醇、異丙醇、丁醇、苄醇、甘油等醇 類； (S> -20- 201209116 丙酮、甲基乙基酮、環戊酮、異弗爾酮等酮類； 甲基乙基醚 '二乙基酸、四氫咲喃、二B惡院等酸類； r-丁內酯、5-丁內酯等內酯類； /3-內醯胺等內醯胺類； 二甲基甲醯胺、N-甲基吡咯烷酮、二甲基乙醯胺等鏈 狀或環狀之醯胺化合物； 亞甲基氰醇、伸乙基氰醇（ethylene cyanohydrin)、 3，3’-硫基二丙腈、乙腈等具有腈基之化合物； 吡啶、吡咯等含氮雜環化合物； 乙二醇、丙二醇等二醇化合物； 二乙二醇、二乙二醇單乙基醚、二乙二醇乙基丁基醚 等二乙二醇或衍生物； 甲酸乙酯、乳酸乙酯、乳酸丙酯、苯甲酸甲酯、乙酸 甲酯、丙烯酸甲酯等酯類等》 本發明之電極用黏合劑組成物中之特定聚合物之含有 比例較好爲20〜60質量％，更好爲25~50質量％ » (增黏劑） 上述增黏劑可含於本發明之電極用黏合劑組成物中用 以進一步提高電極用黏合劑組成物之塗佈性、充放電特性 等。 該等增黏劑可列舉爲例如羧甲基纖維素、甲基纖維素 、羥丙基纖維素等纖維素衍生物； 聚丙烯酸鈉等聚丙烯酸鹽等，以及 -21 - 201209116 聚乙烯醇、聚環氧乙烷、聚乙烯基吡咯烷酮、（甲基 )丙烯酸-乙烯醇共聚物、馬來酸-乙烯醇共聚物、改質聚 乙烯醇、聚乙二醇、乙烯-乙烯醇共聚物、聚乙酸乙烯酯 部份皂化物等。 本發明之電極用黏合劑組成物中之增黏劑含有比例相 對於電極用黏合劑組成物之總固體成分量（組成物中之液 狀介質以外之成分之合計質量）較好爲20重量％以下， 更好爲0.1~10重量％。 (電極用黏合劑組成物之較佳樣態） 本發明之電極用黏合劑組成物較好爲特定聚合物以粒 子狀分散於水性介質中而成之乳膠狀。本發明之電極用黏 合劑組成物最好爲使在水性介質中合成（聚合）如上述之 特定聚合物後之聚合反應混合物視需要調整液性後，將其 直接使用。據此，本發明之電極用黏合劑組成物除聚合物 粒子以及水性介質以外，亦可含有乳化劑、聚合起始劑或 其殘渣、界面活性劑、中和劑等其他成分。該等其他成分 之含有比例，以其他成分之合計重量相對於組成物之固體 成分量之比例計，較好爲3重量％以下，更好爲2重量％ 以下》 電極用黏合劑組成物之固體成分濃度（組成物中之液 狀介質以外之成分之合計質量相對於組成物之總質量所佔 之比例）較好爲20〜60重量％，更好爲25〜50重量％。 至於電極用黏合劑組成物之液性，較好在中性附近， (S> -22- 201209116 更好爲ρΗ6·0~8.5，最好爲 ρΗ7·0〜8 整可使用習知之水溶性酸或鹼。至於 、硝酸、硫酸、磷酸等；鹼可列舉爲 化鉀、氫氧化鋰、氨水等。 本發明之電極用黏合劑組成物含 )及構造單位（Β)之聚合物。因此 了解，可獲得高的黏著性，而且可賦 電率，與高溫環境下之電化學安全性 裝置。 〈電極用漿料〉 本發明之電極用漿料含有電極活 本發明之電極用黏合劑組成物。本發 極活性物質以及本發明之電極用黏合 視需要含有其他成分。 (電極活性物質） 電極活性物質可依據目的之電化 選擇。 本發明之電極用黏合劑組成物使 蓄電池之正極之電極用漿料（正極用 物質（正極活性物質）可使用例如鈷 鋰、磷酸鐵鋰、三元系鎳鈷錳酸鋰等 本發明之電極用黏合劑組成物使 .〇。組成物液性之調 酸可列舉爲例如鹽酸 例如氫氧化鈉、氫氧 有具有構造單位（Α ，由後述之實施例可 予在低溫環境下之放 二者均優異之電化學 性物質，及如上述之 明之電極用漿料除電 劑組成物以外，亦可 學裝置之種類等適當 用於用以形成鋰離子 漿料）時，電極活性 酸鋰、鎳酸鋰、錳酸 〇 用於用以形成鋰離子 -23- 201209116 蓄電池之負極之電極用漿料（負極用漿料）時，電極活性 物質（負極活性物質）可使用例如碳材料、碳等。上述碳 材料可例示爲將有機高分子化合物、焦炭、瀝青等燒成而 獲得之碳材料，該碳材料之前驅物的有機高分子化合物可 列舉爲例如酚樹脂、聚丙烯腈、纖維素等。上述碳可列舉 爲例如人造石墨、天然石墨等。 本發明之電極用黏合劑組成物使用於用以形成電雙層 電容器用之電極之電極用漿料時，作爲電極活性物質可使 用例如石墨、難石墨化碳、硬質碳； 使焦炭、瀝青等燒成而獲得之碳材料； 聚并苯（polyacene)系有機半導體（PAS)等。 (其他成分） 本發明之電極用漿料可依據需要進而含有增黏劑、分 散劑、界面活性劑、消泡劑等。 上述增黏劑可列舉爲與本發明之電極用黏合劑組成物 可任意含有之作爲增黏劑之上述例示者相同者； 上述分散劑可列舉爲例如六偏磷酸鈉、三聚磷酸鈉、 聚丙烯酸鈉等； 上述界面活性劑可列舉爲例如作爲乳膠之安定化劑之 非離子性界面活性劑或陰離子性界面活性劑等。 該等其他成分之含有比例，相對於本發明之電極用漿 料之總固體成分量（組成物中之液狀介質以外之成分之合 計質量），較好爲1〇重量％以下，更好爲0.5〜5重量％ (§> -24- 201209116 (電極用漿料之較佳樣態） 電極用漿料相對於電極活性物質100質量份，電極用 黏合劑組成物以固體成分換算計，較好含有0.1~10質量 份，更好含有0.3〜4質量份。藉由使電極用黏合劑組成物 之含有比例，以固體成分換算計爲0.1〜10質量份，可使 特定聚合物難溶解於電化學裝置中使用之電解液中，其結 果，可抑制因過電壓之上升對裝置特性造成之不良影響。 電極用漿料係藉由混合本發明之電極用黏合劑組成物 、如上述之電極活性物質、及視需要使用之其他成分而調 製。混合該等之手段可利用例如攪拌機、脫泡機、珠粒硏 磨機、高壓均質機等習知之混合裝置。 電極用漿料之調製較好在減壓下進行，藉此，可防止 所得電極活性物質層內產生氣泡》 如上述之電極用漿料藉由含有本發明之電極用黏合劑 組成物，可形成電極活性物質相互間及電極活性物質·集 電體間之密著性高之電極活性物質層，又，可獲得低溫環 境下之放電率與高溫環境下之電化學安定性二者均優異之 電化學裝置。 〈電極〉 本發明之電極具備有： 集電體、 -25- 201209116 經過於前述集電體之表面上塗佈上述說明之電極用漿 料並經乾燥之步驟形成之電極活性物質層。 塗膜經乾燥後，較好進行壓製加工。 (集電體） 集電體可使用例如金屬箔、蝕刻金屬箔、擴張金屬板 (expanded metal )等。該等材料之具體例可列舉爲例如 鋁、銅、鎳、钽、不銹鋼、鈦等金屬，可依據目的之電化 學裝置之種類適當選擇。 例如形成鋰離子蓄電池之正極時，作爲集電體較好使 用上述中之鋁。該情況下，集電體之厚度較好爲5〜3 ，更好爲8〜2 5 // m。 另一方面，形成鋰離子蓄電池之負極時，作爲集電體 較好使用上述中之銅。該情況下，集電體之厚度較好爲 5〜30#m，更好爲 8~25//m。 再者，形成電雙層電容器用之電極時，作爲集電體較 好使用上述中之鋁或銅。該情況下，集電體之厚度較好爲 5〜l〇〇/zm，更好爲 10~70//m，最好爲 15〜30//m。 (電極活性物質層之形成） 電極中之電極活性物質層係經歷在如上述之集電體表 面上塗佈電極用漿料並乾燥之步驟而形成。 對集電體上塗佈電極用漿料之方法可使用例如刮刀塗 佈法、逆輥法、科馬塗佈、凹版印刷法、空氣刀法等適宜 -26- 201209116 之方法。 塗膜之乾燥處理較好在2 0〜2 50。(：，更好在50〜150 °C 之溫度範圍內，進行較好1〜120分鐘，更好5〜60分鐘。 乾燥後之塗膜較好供於壓製加工。進行該壓製加工之 手段可列舉爲例如輥壓製機、高壓超壓製機、軟軋光機、 1噸壓製機等。壓製加工條件係依據使用之加工機種類及 電極活性物質層所需厚度及密度而適宜設定。 電極活性物質層較好爲厚度 40〜100/z m，.密度 1·3~2·0 g/cm3。 (電極之特徵） 如上述形成之電極，由於電極活性物質層使用含有本 發明之黏合劑組成物之電極用漿料而形成，故爲於電極活 性物質層中之電極活性物質相互間及電極活性物質-集電 體間之密著性高者。且，使用該電極時，可獲得在低溫環 境下之放電率特性與高溫環境下之電化學安定性二者均優 異之電化學裝置。 本發明之電極可適用作爲例如鋰離子蓄電池、電雙層 電容器、鋰離子電容器等電化學裝置之電極。 構成鋰離子蓄電池等之蓄電池時，使用本發明之黏合 劑組成物形成之電極可作爲正極亦可作爲負極，且顯示凌 駕過去技術之性能，如由後述之實施例所了解，作爲正極 使用時就獲得更高效果之觀點而言係較佳。 -27- 201209116 〈電化學裝置〉 本發明之電化學裝置具備有如上述之電極。 本發明中之電化學裝置爲具有如上述之電極透過電解 液與對向電極相對，且較好藉由隔離材之存在而隔離之構 造。 至於其製造方法列舉爲例如透過隔離材重疊兩個電極 (正極及負極兩個，或電容用電極兩個），將其捲繞、折 疊成對應於電池形狀等，放入電池容器中，於電池容器中 注入電解液並經封口之方法。電池之形狀可爲硬幣型、鈕 扣型、薄片型、圓筒型、方型、扁平型等適宜之形狀》 上述電解液可依據目的之電化學裝置種類適宜選擇使 用。至於電解液係使用將適當電解質溶解於溶劑中而成之 溶液。 製造鋰離子蓄電池時，係使用鋰化合物作爲電解質。 具體而言，可列舉爲例如LiC104、LiBF4、Lil、LiPF6、 L1CF3SO3、LiAsF6、LiSbF6、L1AICI4、LiCl、LiBr、 LiB(C2H5)4、L1CH3SO3 ' L1C4F9SO3、Li(CF3S02)2N 等。 該情況下之電解質濃度較好爲0.5~3.0莫耳/L，更好爲 0.7〜2.0莫耳/L 。 製造電雙層電容器時，作爲·電解質係使用例如四乙基 銨四氟硼酸鹽、三乙基甲基銨四氟硼酸鹽、四乙基銨六氟 硫酸鹽等。該情況下之電解質濃度較好爲〇.5~3.〇莫耳/L ，更好爲0.7~2.0莫耳/L。 製造鋰離子電容器時之電解質種類及濃度與鋰離子蓄 -28- 201209116 電池之情況相同。 上述任一情況中，電解液中使用之溶劑均可列舉爲例 如碳酸丙烯酯、碳酸乙烯酯、碳酸丁烯酯、碳酸二甲酯、 碳酸二乙酯、碳酸甲酯乙酯等碳酸酯； r-丁內酯等之內酯； 三甲氧基矽烷、ι，2-二甲氧基乙烷、二乙基醚、2_乙 氧基乙烷、四氫呋喃、2 -甲基四氫呋喃等醚類； 二甲基亞颯等亞楓類； 1，3-二氧雜環戊烷、4-甲基-1，3-二氧雜環戊烷等氧雜 環戊烷衍生物； 乙腈、硝基甲烷等含氮化合物； 甲酸甲酯、乙酸甲酯、乙酸丁酯、丙酸甲酯、丙酸乙 酯、磷酸三酯等酯類； 二乙二醇二甲醚、三乙二醇二甲醚（triglyme)、四 乙二醇二甲醚等之乙二醇二甲醚化合物； 丙酮、二乙基酮、甲基乙基酮、甲基異丁基酮等酮類 » 環丁碼等颯化合物； 2-甲基-2-噁唑啶酮等噁唑啶酮衍生物； 1,3-丙烷磺內酯、1，4-丁烷磺內酯、2,4-丁烷磺內酯 、：l，8-萘磺內酯等磺內酯化合物等。 該等電化學裝置之電極活性物質層中之電極活性物質 相互間與電極活性物質-集電體間之密著性高，而且，在 低溫環境下之放電率特性、及高溫環境下之電化學安定性 -29- 201209116 兩者均優異。據此，該電化學裝置除適用作爲搭載於電動 車、油電混合車、卡車等汽車上之蓄電池或電容器以外’ 亦可使用作爲AV設備、OA設備、通信設備等中使用之 蓄電池、電容器。 實施例 以下例示實施例及比較例具體說明本發明。然而本發 明並不限於該等實施例。 以下之實施例及比較例中之「份」若未特別說明則爲 質量基準。 以下實施例及比較例中之電極及電化學裝置之評價方 法分別如下述。 〈電極之評價〉 (1 )電極活性物質層之剝離強度 自電極（層合體）切割出寬度2 cm X長度12 cm之試驗 片。將該試驗片之電極活性物質層側之表面以雙面膠帶貼 合於鋁板上。於鋁板上之試驗片之集電體側表面上貼合寬 度18mm之膠帶（JIS Z 1 522標準品，商品名「Cellotape (註冊商標）」，Nichiban (股）製造）。 一面使與鋁板之角度維持在90°，一面使該膠帶朝上 方以50mm/分鐘之速度上拉，測定以剝離角度90°剝離時 之剝離強度（mN/km) 6次，算出其平均値作爲電極活性 物質層之剝離強度（mN/2cm )。又「mN/2cm」爲表示毎 201209116 2cm之剝離強度之單位。 剝離強度之値愈大，則集電體與電極活性物質層之密 著強度愈高，可判斷愈難自集電體剝離電極活性物質層。 尤其，該値在90mN/2cm以上時爲良好。 〈鋰離子蓄電池之評價〉 (1 )低溫率特性（3.0C/0.2C ) 首先，使鋰離子蓄電池在-2(TC以定電流（0.2C ) · 定電壓（3.8V)之方式充電、以定電流（0.2C)之方式放 電爲一循環，測定重複3次循環後之放電電容（CQ. 2 )。 接著，測定使該電池在-20°C以定電流（0.2C ).定電壓 (3.8V)之方式充電，以定電流（3.0C)之方式放電時之 放電電容（C 3. 〇 )。 使用該測定値，以下述式算出鋰離子蓄電池之低溫率 特性（3.0C/0.2C) ( % )。 低溫率特性（％) = {(C3. 〇) + (C〇. 2)} X 1 0 0 該低溫率特性之値愈大，可判斷在低溫環境下之電極 特性變化愈小。尤其，該値爲80%以上時爲良好。 又，測定條件中之「1 C」係表示具有某一定電容之電 池經定電流放電於1小時成爲放電結束之電流値。例如「 0.1C」意指經10小時成爲放電結束之電流値，10C意指 經0.1小時成爲放電結束之電流値。 (2)高溫環境下之自行放電率 -31 - 201209116 首先，測定使鋰離子蓄電池於常溫（25 °C )以定電流 (0-2C ) •定電壓（3.8V)之方式充電，以定電流（0.2C )之方式放電時之放電電容（C。接著，測定使該電 池在常溫（25°C)以定電流（0.2C).定電壓（3.8V)之 方式充電，在85°C靜置3天後，已放冷至常溫（25°C )後 以定電流（0.2C)之方式放電時之放電電容（C :^)。 使用該等測定値，由下式算出自行放電率（％)。 自行放電率（％) = [{(C之前）一（C之後）} + (C之前）]X100 該自行放電率値愈小，可判斷愈可抑制高溫環境下之 自行放電。尤其，該値未達3 0%時爲良好。 (3 )循環特性 使鋰離子蓄電池以定電流（0_2C ).定電壓（3.8V) 之方式充電，以定電流（0.2C )之方式放電爲一循環，重 複5〇次。測定第3次循環之放電電容（C3(fiiB)及第50次 循環之放電電容（C 5〇_)，由下式算出循環特性（％ )。 循環特性（％) = {(C50循環）+ (C3循環)} XI 00 該循環特性値愈接近1 00%，可判斷愈可抑制因充放 電引起之黏合劑氧化分解等所導致之電池特性劣化。尤其 該値爲8 0 %以上時爲良好。 〈電雙層電容器之評價〉 (1)高溫環境下之自行放電率（％) 測定使電雙層電容器在常溫（25°c )以定電流（ -32- 201209116 1 OmA/F ).定電壓（2.5V)之方式充電1小時後之電壓 (V趙）。接著，測定使該電雙層電容器在85°c放置3天 後之電壓（Vta)。 使用該等測定値，由下式算出自行放電率（％)。 自行放電率⑻=[{(V之前）-(V之後）} + (V之前)]X10 0 該上述自行放電率値愈小，可判斷愈可抑制在高溫環 境下之自行放電。尤其該値未達30%時爲良好。 (2)循環特性 使電雙層電容器以定電流（1C) ·定電壓（3.5V)之 方式充電，以定電流（1C)之方式放電爲一循環重複100 次循環。此時，測定第3次循環之放電電容（C3_)及第 1〇〇次循環之放電電容（Cnwes)，由下式算出循環特性（ % )。 循環特性（％) = {(C100循頊）+ (C3循環)} χιοο 該循環特性値愈接近1 00%，可判斷愈可抑制因充放 電引起之黏合劑氧化分解等所導致之電池特性劣化。尤其 該値爲8 0 %以上時爲良好。 〈電極用黏合劑組成物之調製例〉 實施例1 將水150份及十二烷基苯磺酸鈉0.2份饋入容量7升 之可分離燒瓶中，以氮氣充分置換可分離燒瓶內部。 另一方面，於另一容器中添加水60份、換算固體成 -33- 201209116 分爲0.8份之作爲乳化劑之醚硫酸酯型乳化劑（商品名「 ADEKA REASOAP SR 1 025」，ADEKA (股）製造）、及 作爲單體之甲基丙烯酸2,2,2-三氟乙酯25份、丙烯腈25 份、甲基丙烯酸甲酯10份、甲基丙烯酸2-乙基己酯40 份及甲基丙烯酸5份，並經充分攪拌，調製含有上述單體 混合物之單體乳化液。 隨後，使上述可分離燒瓶之內部開始升溫，在該可分 離燒瓶之內部溫度到達60 °C之時點，添加作爲聚合起始劑 之過硫酸銨0.5份。接著，在可分離燒瓶之內部溫度到達 7 0°C之時點，開始添加上述調製之單體乳液，使可分離燒 瓶之內度溫度維持在70°C下，於3小時內緩慢添加單體乳 化液。隨後，使可分離燒瓶之內部溫度上升至85 °C，在該 溫度維持3小時進行聚合反應。3小時後，將可分離燒瓶 冷卻並終止反應後，添加氨水將pH調整成7.6，調製電 極用黏合劑組成物（s 1 )。 所得電極用黏合劑組成物（s 1 )之固體成分濃度爲 30質量％。電極用黏合劑組成物（si)中之聚合物爲玻 璃轉移溫度係-10°C，數平均粒徑係100nm之粒子狀。 實施例2~6及比較例1〜5及7 除依循下述表1中所示之調配處分使用單體以外，餘 與實施例1同樣實施，分別調製電極用黏合劑組成物（s2 )~ ( s6)及（r1 )〜（r5 )及（r7)。 所得各電極用黏合劑組成物中之聚合物之玻璃轉移溫 (S) -34- 201209116 度及聚合物粒子之數平均粒徑一起列於下表1<( 實施例7 將水150份及十二烷基苯磺酸鈉〇.2份饋入容量7升 之可分離燒瓶中，以氮氣充分置換可分離燒瓶內部。 另一方面，於另一容器中添加水60份、換算固體成 分爲0.8份之作爲乳化劑之醚硫酸酯型乳化劑（商品名「 ADEKA REASOAP SR 1 025」，ADEKA (股）製造）、及 作爲單體之甲基丙烯酸2,2,2-三氟乙酯25份、丙烯腈25 份、甲基丙烯酸甲酯10份、甲基丙烯酸2-乙基己酯40 份及甲基丙烯酸5份，並經充分攪拌，調製含有上述單體 混合物之單體乳化液。 將該單體乳化液之全量添加於上述可分離燒瓶中之後 ，開始升溫，在該可分離燒瓶之內部溫度到達6(TC之時點 ，添加作爲聚合起始劑之過硫酸銨0.5份。接著，使可分 離燒瓶之內部溫度升溫達70t，且維持該溫度3小時後， 使溫度升溫至8 5 °C進行聚合反應3小時。隨後，將可分離 燒瓶冷卻並終止反應後，添加氨水將pH調整成7.6，調 製電極用黏合劑組成物（s7 )。所得電極用黏合劑組成物 (s7)之固體成分濃度爲30質量％。電極用黏合劑組成 物（s7 )中之聚合物爲玻璃轉移溫度係_丨ot，數平均粒 徑係100nm之粒子狀。 比較例6 -35- 201209116 除依循下表1所示之調配處分使用單體以外，餘與上 述實施例7同樣實施，調製電極用黏合劑組成物（r6 )。 所得電極用黏合劑組成物（r6 )中之聚合物之玻璃轉 移溫度及聚合物粒子之數平均粒徑一起列於下表1。 實施例8 於具備攪拌機之溫度可調節之高壓釜中，一次饋入水 200份、十二烷基苯磺酸鈉〇_6份、過硫酸鉀1.0份及亞 硫酸氫鈉〇·5份，以及作爲單體之甲基丙烯酸2,2,2-三氟 乙酯25份、丙烯腈25份' 苯乙烯16份、丁二烯35份及 甲基丙烯酸4份，在80°C進行聚合反應6小時，獲得聚合 物分散液。隨後，於所得聚合物分散液中添加氨水溶液將 pH調整成7.4，添加作爲增黏劑之聚丙烯酸鈉1份後，以 水蒸氣蒸餾對殘留單體進行去除處理後，於減壓下將固體 成分濃度濃縮至48質量％，藉此調製電極用黏合劑組成 物（s8 ) » 所得電極用黏合劑組成物（s 8 )中之聚合物之玻璃轉 移溫度及聚合物粒子之數平均粒徑一起列於下表1。 比較例8 除依循下表1所示之調配處分使用單體外，餘與上述 實施例8同樣實施，調製電極用黏合劑組成物（r8 )。 所得電極用黏合劑組成物（r8 )中之聚合物之玻璃轉 移溫度及聚合物粒子之數平均粒徑一起列於下表1。 -36- 201209116 麗·Ν%ι^ίi 實施例8 1 CO (/> 〇 〇 CM o LO CM JO ο ο CO ιο C0 ο 〇 σ> σ> 實施例7 卜 υ> S 〇 。 in eg o ir> CM tn ΙΟ ο ο ο ο ο CO ο 實施例6 to (0 S 〇 。 o LO CM IT) CM in in ο ο ο ο ο ο ο 實施例5 ιο Μ 〇 〇 s in cs 〇 in CM in m ο ο ο ο ο ο S 實施例4 兮 (Λ 〇 ° 8 in CS| o LO CV4 JO IT) ο ο ο ο ο ο σ> σ> 實施例3 Γ〇 (A S 〇 。 s ir> o (O in m tn ο ο ο ο ο ο S 實施例2 CM (0 〇 〇 。 o o o s lO tn eg S ο ο ο ΙΟ S τ*~ 實施例1 : 〇 〇 s in CM o lO CM § in Ο ο ο ο ο ο C0 σ> I黏合劑組成物名稱 甲基丙烯酸2,2,2-三氟乙酯 t丙烯酸2,2,2-三氟乙酯 丙烯酸1,1,1,3,3,3-六氟異丙醋 構造單位(A)之含有比例 丙烯腈 甲基丙烯腈 構造單位(B)之含有比例 構造單位(A)+構造單位(B) 甲基丙烯酸 甲基丙稀酸甲酯 甲基丙烯酸2-乙基己酯 苯乙烯 丁二烯 乙二醇二甲基丙烯酸酯 1聚合物之玻璃轉移溫度(°c) 1聚合物粒子之數平均粒徑(ηπι) s 2* Q 其他 (卿 術 I) -37- 201209116 8麗N霞囊— s 比較例8 1 00 m 〇 〇 m 〇 o ο in 卜 in 〇 CO CO 5 〇 〇 g 比較例7 卜 ο 〇 〇 〇 m o in in if> ο S 〇 〇 〇 § 1 ο 比較例6 CO s 〇 〇 〇 o ο s ο 〇 〇 C0 00 C0 ο 比較例5 in 8 〇 〇 〇 o ο s m ο 泛 〇 〇 CO 1〇 C0 1 s 比較例4 寸 CM in 〇 〇 CM ΙΟ ιο CM o in CO ο 8 〇 〇 〇 ο 比較例3 CO LO CD 〇 〇 ΙΟ (D LO o in o CO ο 〇 〇 〇 m CO 比較例2 CM o 〇 〇 Ο 9 o CM it> in ο 〇 〇 〇 CM s 比較例1 CO 〇 〇 CO CO o CO to m ιη CM S 〇 〇 〇 in CVJ s 組成物名稱 I 甲基丙烯酸2,i2-三氟乙酯 丙烯酸2,2,2-三氟乙酯 丙烯酸U,1,3,3,3-六氟異丙酯 構造單位(Α)之含有比例 丙烯腈 甲基丙烯腈 構造單位(B)之含有比例 構造單位(八)增造單位(B) 甲基丙烯酸 甲基丙烯酸甲酯 甲基丙烯酸2-乙基己酯 苯乙烯 丁二烯 乙二醇二甲基丙烯酸酯 1聚合物之玻璃轉移溫度(°c) 1聚飾粒子之數平均粒徑(nm) <Π m 圈 tfwml φΠΓ g s ㊀ Q 其他 (扮)迪锇翳亩 -1- -38- 201209116 〈鋰離子蓄電池之製造及評價（1)，本發明之電極用黏 合劑組成物使用於正極中之例〉 實施例9~ 1 5及比較例9~ 1 5 使用上述實施例1〜7及比較例1〜7中調製之電極用黏 合劑組成物（si)〜（s7)及（rl)〜（Γ7)，如下述製造 鋰離子蓄電池並fF價。 (1)鋰離子蓄電池用正極之製造 於雙軸型班伯里混練機（商品名「TK HIVIS MIX 2P-03」，PRIMIX (股）製造）中注入增黏劑（商品名「 CMC8 00H」，DAICEL化學工業（股）製造）1份（換算 固體成分）、作爲正極活性物質之磷酸鐵鋰100份（換算 固體成分）、作爲導電劑之乙炔黑5份（換算固體成分） 及水70份，以60rpm進行攪拌1小時。隨後，添加上述 實施例及比較例中調製之各電極用黏合劑組成物2份（換 算固體成分），進而攪拌1小時獲得糊料。於所得糊料中 追加水90份，將固體成分濃度調整成40質量％後，使用 攪拌脫泡機（商品名「AWATORY練太郎」，THINKY ( 股）製造），以200rpm攬拌2分鐘，接著以l，800rpm攪 拌5分鐘，再於減壓下以l，800rpm攪拌·混合1.5分鐘 ’調製正極用漿料。 接著，於厚度30//m之由鋁箔構成之集電體表面上 ，以使乾燥後之塗膜膜厚成爲90/zm之方式’以刮板塗 佈法均句塗佈上述調製之正極用漿料’在120 °C下乾燥20 -39- 201209116 分鐘，獲得塗膜。隨後，以使膜之密度成爲1.7g/cm3之 方式，使用輥壓製機進行壓製加工，形成電極活性物質層 而形成層合體。藉由對該層合體進行沖壓加工，製造直徑 15.95 mm之圓盤狀鋰離子蓄電池用正極。 所得各鋰離子蓄電池用正極中之電極活性物質層之剝 離強度示於下表2。 (2)鋰離子蓄電池用負極之製造 於雙軸型班伯里混練機（PRIMIX (股）製造，商品 名「TK HIVIS MIX 2P-03」）中注入聚偏氟化乙烯（ PVDF )4份（換算固體成分）、作爲負極活性物質之石 墨100份（換算固體成分）、N-甲基吡咯烷酮（NMP) 80 份，以60rpm進行攪拌1小時。隨後，再投入NMP 20份 後，使用攪拌脫泡機（THINKY (股）製造，商品名「 AWATORY練太郎」），以200'rpm攪拌2分鐘，接著以 l，800rpm攪拌5分鐘，再於減壓下以l，800rpm攪拌·混 合1.5分鐘，調製負極用漿料。 接著，於厚度20^m之由銅箔構成之集電體表面上 ’以使乾燥後之塗膜膜厚成爲1 50 a m之方式，以刮板塗 佈法均勻塗佈上述調製之負極用漿料，在120°C乾燥20分 鐘，獲得塗膜。隨後，以使膜之密度成爲1.8g/cm3之方 式，使用輥壓製機進行加工，形成層合體。藉由對該層合 體進行沖壓加工，製造直徑16.16mm之圓盤狀鋰離子蓄 電池用負極。 (S> -40- 201209116 (3)鋰離子蓄電池之製造 於手套箱中，將鋰離子蓄電池用負極載置於二極式硬 幣電池（商品名「HS平板電池（flat cell)」，寶泉（股 )製造）上。接著於該負極上載置直徑18mm之圓盤狀之 由聚丙烯製多孔膜構成之隔離材（商品名「CELGARD #2400」’CELGARD (股）製造），接著以不使空氣進入 之方式注入電解液。接著，於該隔離材上載置鋰離子蓄電 池用正極後，以螺絲鎖上前述2極式硬幣電池之外殼並密 封，製造鋰離子蓄電池。 此處使用之電解液係將LiPF6以濃度lmol/L之濃度 溶解於碳酸乙烯酯/碳酸乙酯甲酯=1/1(質量比）之溶劑 中而成之溶液。 所得各鋰離子蓄電池之低溫率特性、高溫環境下之自 行放電率及循環特性示於下表2。 -41 - 201209116 實施例15 〇 s in s 實施例14 CO (Λ C0 05 s CO CM in CO 實施例13 LO (0 〇i σ> s eg m CO *施例12 寸 U) CM ay s ci in CO 實施例11 C0 V) S s CM o 實施例10 CM V) CO σ> Si lO CM σ> 實施例9 (/> S a σϊ 黏合劑物名稱 |電極活性物質層之剝離強度_/2cm) I倾率特14(%) |高溫環境下之白行放電率(％) 循環特性(％) 比較例15 | 卜 5 m ιο σ> CP 比較例14 ο s 比較例13 in s in CO 比較例12 : S 另 in 00 比較例11 s ai 比較例10 S s 5； 比較例9 λ- S CO |黏合劑組成物名稱 I電極活性物質層之剝離強度(mN/2cm) |低溫率特性(%) 髙溫環境下之自行放電率(％) |循環特14(%) 42- 201209116 由表2之結果可知，使用本發明之電極用黏合劑組成 物（si )〜（s7 )時，獲得電極活性物質層之剝離強度高 之鋰離子蓄電池用正極。而且’確認具備該種正極之鋰離 子蓄電池爲在低溫環境下之放電率特性、及在高溫環境下 之電化學安定性兩者均優異者。 尤其，使用甲基丙烯酸2,2,2-三氟乙酯作爲特定含氟 (甲基）丙烯酸酯，使用丙烯腈作爲不飽和腈化合 物之電極用黏合劑組成物（si) ~(s3) ’獲得電極活性 物質層之剝離強度更高之鋰離子蓄電池用正極’而且確認 獲得在低溫環境下之放電率特性及高溫環境下之電化學安 定性更優異之鋰離子蓄電池。 〈鋰離子蓄電池之製造及評價（2)，本發明之電極用黏 合劑組成物使用於負極中之例〉 實施例16〜18及比較例16〜18 分別使用上述實施例1、7及8以及比較例5、6及8 中調製之電極用黏合劑組成物（si ) 、（ s7 )及（s8 )以 及（r5)~(r6)及（r8)，如下述製造鋰離子蓄電池並 評價。 (1)鋰離子蓄電池用負極之製造 於雙軸型班伯里混練機（商品名「tk hi vis mix zp-cn 」 ，PRIMIX (股）製造）中投入增黏劑（商品名「 CMC22 00」，DAICEL化學工業（股）製造）1份（換算 -43- 201209116 固體成分）、作爲負極活性物質之石墨100份（換算固體 成分）及水68份，以60rpm進行攪拌1小時。隨後，添 加上述實施例及比較例中調製之各電極用黏合劑組成物1 份（換算固體成分），再攪拌1小時獲得糊料。於所得糊 料中追加水34份，將固體成分濃度調整成50質量％後， 使用攪拌脫泡機（商品名「AWATORY練太郎」， THINKY (股）製造），以200rpm攪拌2分鐘，接著以 l，800rPm攪拌5分鐘，再於減壓下以l,800rpm攪拌.混 合1.5分鐘，藉此調製負極用漿料。 接著，於厚度20/zm之由銅箔構成之集電體表面上 ，以使乾燥後之塗膜膜厚成爲80#m之方式，以刮板塗 佈法均勻塗佈上述調製之負極用漿料，在120°C乾燥20分 鐘，獲得塗膜。隨後，以使膜之密度成爲1.8g/cm3之方 式，使用輥壓製機進行壓製加工，形成電極活性物質層而 形成層合體。藉由對該層合體進行沖壓加工，製造直徑 16.16mm之圓盤狀鋰離子蓄電池用負極。 所得各鋰離子蓄電池用負極中之電極活性物質層之剝 離強度示於下表3。 (2)鋰離子蓄電池用正極之製造 於雙軸型班伯里混練機（商品名「TK HI VIS MIX 2P-〇3」，PRIMIX (股）製造）中投入聚偏氟化乙烯5份（ 換算固體成分）、作爲正極活性物質之磷酸鐵鋰100份（ 換算固體成分）、作爲導電劑之乙炔黑5份（換算固體成 (§> -44 - 201209116 分）及N-甲基吡咯烷酮（NMP ) 25份，以6〇rpm進行攪 拌1小時。接著，再投入NMP 10份後，使用攪拌脫泡機 (商品名「AWATORY練太郎」，THINKY (股）製造） ’以20〇rpm攪拌2分鐘，接著以l，800rpm攪拌5分鐘， 再於減壓下以l，8 00rpm攪拌·混合1.5分鐘，調製正極 用漿料。 接著，於厚度3〇vm之由鋁箔構成之集電體表面上 ’以使乾燥後之塗膜膜厚成爲90 m之方式，以刮板塗 佈法均勻塗佈上述調製之正極用漿料，在12(TC乾燥20分 鐘，獲得塗膜。隨後，以使膜之密度成爲1.7g/cm3之方 式，使用輥壓製機進行壓製加工，形成電極活性物質層而 形成層合體。藉由對該層合體進行沖壓加工，製造直徑 15.95mm之圓盤狀鋰離子蓄電池用正極。 (3)鋰離子蓄電池之製造 除使用上述製造之負極及正極以外，餘與上述實施例 9〜1 5及比較例9〜1 5同樣，製造鋰離子蓄電池，並評價。 評價結果示於表3。 -45- 201209116 比較例18 | 00 CM 00 S CM CO CNJ CO 比較例17 CO CO 00 σ> CO in CNJ 比較例16 1〇 § CO CO a> CNJ s 實施例18 〇〇 V) σ> ⑦ CO 03 CsJ σ> 實施例17 卜 V) g τ— § CO 實施例16 ο in σ> in in σ> |黏合劑組成物名稱 1電極活性物質層之剝離強度(mN/2cm) 倾率特性(％) 髙溫環境下之自行放電率(％) 循環特性(％) i) -46- 201209116 如由表3之結果所理解，使用本發明之電極用黏合劑 組成物（si ) 、（ s7 )及（s8 )時，可獲得電極活性物質 層之剝離強度高之鋰離子蓄電池用負極。因此，具備該種 負極之鋰離子蓄電池確認爲在低溫環境下之放電速特性、 及在高溫環境下之電化學安定性兩者均優異者。 但，與本發明之電極用黏合劑組成物使用於鋰離子蓄 電池用正極中之情況相比較時，關於低溫率特性及高溫環 境下之自行放電率，於實施例及比較例間之差異小（參照 上述表2)。由此，可知本發明之電極用黏合劑組成物將 其使用於正極中時可獲得更大之效果。 〈電雙層電容器之製造及評價，本發明之電極用黏合劑組 成物使用於電容器用電極中之例〉 實施例19及20以及比較例19〜21 (1)電雙層電容器用電極之製造 於雙軸型班伯里混練機（商品名「TK HI VIS MIX 2P-03」，PRIMIX (股）製造）中投入作爲電極活性物質之 活性碳（商品名「KURARAY COAL YP」’ KURARAY CHEMICAL (股）製造）1 〇〇份、導電性碳（商品名「 DENKA BLACK」，DENKA電化學工業（股）製造）6份 、增黏劑（商品名「CMC2200」，DAICEL化學工業（股 )製造）2份及水2W份’以60rpm進行攪拌1小時。隨 後，添加上述實施例及比較例中製造之各電極用黏合劑組 成物4份（換算固體成分）’再攪拌1小時獲得糊料。於 -47 - 201209116 所得糊料中追加水58份，將固體成分濃度調整成25質量 %後，使用攪拌脫泡機（商品名「AWATORY練太郎」， THINKY (股）製造），以200rpm攪拌2分鐘，接著以 l，800rpm攪拌5分鐘，再於減壓下以l，800rpm攪拌·混 合1.5分鐘，調製電極用漿料。 接著，於厚度20#m之由鋁箔構成之集電體表面上 ，以使乾燥後之塗膜膜厚成爲150/ζπι之方式，以刮板塗 佈法均勻塗佈上述調製之正極用漿料，在120°C乾燥20分 鐘，獲得塗膜。隨後，以使膜之密度成爲1.5g/cm3之方 式，使用輥壓製機進行壓製加工，形成電極活性物質層而 形成層合體。藉由對該層合體進行沖壓加工，製造直徑 15.59mm及16.16mm之兩種圓盤狀電雙層電容器用電極 〇 所得電雙層電容器用電極中之電極活性物質層之剝離 強度示於下表4。 (2)電雙層電容器之製造及評價 於手套箱中，將直徑16.16mm之電雙層電容器用電 極載置於二極式硬幣電池（商品名「HS平板電池」，寶 泉（股）製造）上。接著於該電極上載置直徑18mm之圓 盤狀之由纖維素系隔離材（商品名「TF4535」，NIPPON 高度紙工業（股）製造），接著以不使空氣進之方式注入 電解液。接著，於該隔離材上載置直徑15.95mm之電雙 層電容器用電極後，以螺絲鎖上前述2極式鎳幣電池之外 -48- 201209116 殻並密封，製造電雙層電容器。 此處使用之電解爲含有lmol/L濃度之三乙基甲基銨 四氟硼酸鹽之碳酸丙烯酯溶液。 所得各電雙層電容器之高溫環境下之自行放電率及循 • 環特性示於下表4。 -49- 201209116 比較例21 | 卜 04 00 00 比較例20 CO 民 CO C0 (Ο 比較例19 in r- 實施例20 g CSJ 00 實施例19 s 〇 |黏合劑組成物名稱 I電極活物質層之剝離強度(mN/2cm) I髙温環境下之自行放電率(％) 循環特性(％) S3!寸嗽) (S> 50- 201209116 由表4之結果可知，使用本發明之電極用黏合劑組成 物（si)及（s7)時，可獲得在低溫環境下之放電率特性 及高溫環境下之電化學安定性兩者均優異之電雙層電容器 -51 -[Embodiment] The electrode binder composition of the present invention is described in detail below. <Binder composition for electrode> The electrode binder composition of the present invention contains a monomer derived from the above general formula (I). The structural unit (A) and the polymer derived from the structural unit (Β) of the α,β-unsaturated nitrile monomer (hereinafter referred to as "specific polymer"). The electrode binder composition may further contain a liquid medium and may contain any tackifier. The electrode binder composition of the present invention may further contain other components such as an emulsifier, a polymerization initiator or a residue thereof, a surfactant, a neutralizing agent, and the like. [Specific polymer] The specific polymer contained in the electrode binder composition of the present invention has a structural unit (Α) and a structural unit (Β). The specific polymer may have other structural units in addition to the structural unit (Α) and the structural unit (Β). (Structural unit (A)) The specific polymer in the present invention has a structural unit (A) derived from the monomer represented by the above general formula (1). -8-201209116 R2 in the above general formula (1) may, for example, be a fluorinated alkyl group having a carbon number of 1818 or a fluorinated aryl group having a carbon number of 6 to 18, a fluorine aromatic group having a carbon number of 7 to 18, or the like. . R2 is preferably a fluorinated alkyl group having 1 to 11 carbon atoms, and is preferably a group represented by the following general formula (2). Η ~C-R3 (2) R4 (However, R3 represents a hydrogen atom or a fluorinated hydrocarbon group having 1 to 1 carbon atoms, and R4 represents a fluorinated hydrocarbon group having 1 to 1 carbon atom). The fluorinated hydrocarbon group having 1 to 10 carbon atoms of R3 and R4 in the above general formula (2) is preferably a fluorinated alkyl group having 1 to 10 carbon atoms. Preferred specific examples of the group represented by the above general formula (2) are, for example, 2,2,2-trifluoroethyl, 1,1,1-trifluoropropan-2-yl, 2-(perfluorooctyl) Ethyl, 2,2,3,3-tetrafluoropropyl, 2,2,3,4,4,4-hexafluorobutyl, 1H,1H,9H-perfluoro-didecyl, 1H, 1H-11H - perfluoroundecyl, perfluorooctyl, etc., more preferably 2,2,2-trifluoroethyl and 2,2,2-trifluoroisopropyl, preferably 2,2, 2-Trifluoroethyl. . In the above general formula (2), R3 is preferably a hydrogen atom, and R4 is a gasification base having a carbon number of 1-3. The monomer which is introduced into the structural unit (A) and which is represented by the above general formula (1) may be used alone or in combination of two or more selected from the above. (Structural unit (B)) -9-201209116 The specific polymer of the present invention has the above structural unit (A) and has a structural unit (B) derived from an α,/3-unsaturated nitrile monomer. In the case of introducing a structural unit (Β): Specific examples of the /?-unsaturated nitrile monomer include, for example, (meth)acrylonitrile, α-chloroacrylonitrile, and vinyl cyanide. Among these, (meth)acrylonitrile or the like is preferable, and acrylonitrile is more preferable. These α,/3-unsaturated nitrile monomers may be used alone or in combination of two or more. (Types of Other Structural Units) As described above, the specific polymer in the present invention may have other structural units in addition to the structural unit (Α) and the structural unit (Β). These other structural units can be exemplified by the structural unit (C) ' derived from the unsaturated carboxylic acid monomer' - the above-mentioned group of the 澧SH singles constructed from the source D-single澧SB 单 基 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙 乙However, 'R5 represents a hydrogen atom or a methyl group 'R6 represents a hydrocarbon group of a carbon number) -10- 201209116 Step of introducing a structural unit (C) The saturated carboxylic acid monomer may, for example, be an unsaturated monocarboxylic acid or an unsaturated dicarboxylic acid. Monoalkyl ester of unsaturated dicarboxylic acid, monodecylamine of unsaturated dicarboxylic acid, and the like. The monocarboxylic acid may, for example, be (meth)acrylic acid or crotonic acid. The above unsaturated dicarboxylic acid may, for example, be maleic acid, fumaric acid or itaconic acid. The monocarboxylic system of the unsaturated carboxylic acid introduced into the structural unit (C) is, as described above, preferably (meth)acrylic acid and itaconic acid, preferably methacrylic acid. These unsaturated carboxylic acid monomers may be used alone or in combination of two or more. R6 in the above general formula (3) is preferably an alkyl group having 1 to 12 carbon atoms, and examples thereof include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a n-pentyl group. , isoamyl, n-hexyl, 2-ethylhexyl, n-octyl, isodecyl, n-decyl, and the like. The monomers represented by the above general formula (3) which are introduced into the structural unit (D) may be used singly or in combination of two or more. In the monomer introduced into the structural unit (E), examples of the conjugated diene include 1,3-butadiene, 2-methyl-, 3-butanediyl (isoprene). 2,3-dimethyl-1,3-butadiene, 2-chloro-1,3-butadiene (chloroprene), etc.» As for the aromatic vinyl monomer, for example, styrene, α -methylstyrene, p-methylstyrene, vinyltoluene, chlorostyrene, divinylbenzene, and the like. The monomer introduced into the structural unit (Ε) may be used alone or in combination of two or more of -11 - 201209116. Examples of the other monomer introduced into the structural unit (F) include hydroxyalkyl (meth)acrylate such as hydroxymethyl (meth)acrylate and hydroxyethyl (meth)acrylate; and ethylene glycol di(meth)acrylic acid. a polyfunctional (meth) acrylate monomer such as an ester; a vinyl carboxylate such as vinyl acetate or vinyl propionate; an acid anhydride of an unsaturated dicarboxylic acid; and a hydrazine, a hydrazinyl enamine. The propionic acid is a carboxylic acid group and the two methyl group is a non-amined one; the amine of the amine is diamined, the monoamine amine is selected, and the like is an acid enene. The base group and the ethyl ketone can be used as the amine group, the amine group such as the base group, and the amine group (the ratio of the constituent units in the specific polymer). The content ratio of the structural unit (A) in the specific polymer is 5 of the total structural units. ~60% by mass, preferably 7 to 55% by mass. When the content ratio of the structural unit (A) is too small, the cycle characteristics of the obtained electrochemical device are lowered. On the other hand, when the content ratio of the structural unit (A) is too large, there is a case where it is difficult to form an electrode active material layer having high adhesion to the current collector. The content ratio of the structural unit (B) in the specific polymer is all 5 to 40% by mass in the structural unit, preferably 5 to 35% by mass. When the content ratio of the structural unit (B) is too small, the self-discharge of the obtained electrochemical device when stored in a high-temperature environment becomes large, and the durability is low. -12 - 201209116 On the one hand, when the content ratio of the structural unit (B) is too large, the obtained electrode active material layer tends to be hard and brittle, and the adhesion or flexibility to the current collector is low. . In the specific polymer of the present invention, the total content of the structural unit (A) and the structural unit (B) is from 1 to 70% by mass, preferably from 15 to 65% by mass, based on the total of the structural units. When the ratio is within the above range, the discharge rate characteristics in a low-temperature environment and the electrochemical stability in a high-temperature environment can be further improved, so that the specific polymer in the present invention has a structural unit (A) and a structural unit (B). In the case of the structural unit (C), when the binder composition of the present invention is mixed with the electrode active material, the electrode active material does not aggregate, and a slurry for an electrode having excellent dispersibility of the electrode active material can be produced. On the other hand, when the content ratio of the structural unit (C) is too large, the oxidation resistance of the specific polymer is deteriorated, so that the polymer is deteriorated by oxidative degradation due to repeated charge and discharge, and the electrode active material layer cannot be maintained. As a result, it occurs. The disadvantage of the deterioration of the charge and discharge characteristics over time. In view of such a case, the content ratio of the structural unit (C) in the specific polymer is preferably 10% by mass or less, more preferably 3% by mass, based on the entire structural unit. 'The electrode binder composition containing a specific polymer having a structural unit (A) and a structural unit (B) and a structure 'unit (D) is used between the current collector and the electrode active material layer when it is used for the electrode of the positive electrode or the capacitor. The advantage of improved adhesion. On the other hand, in the specific polymer having a too large proportion of the structural unit (D), the ionic conductivity and the oxidation resistance are deteriorated, and as a result, there is a possibility that the electrode resistance rises and the charge and discharge characteristics deteriorate over time. 201209116 points. In view of the above, the content ratio of the structural unit (D) in the specific polymer is preferably 90% by mass or less, more preferably 25 to 80% by mass, based on the entire structural unit. When an electrode binder composition containing a specific polymer having a structural unit (A) and a structural unit (B) and a structural unit (E) is used for a negative electrode, a carbon material (for example, graphite) which is generally used as a negative electrode active material is produced. Etc.) has the advantage of moderate adhesion. Further, the obtained electrode layer is soft or has good adhesion to the current collector. On the other hand, when the content ratio of the structural unit (E) is too large, the ionic conductivity and oxidation resistance of the specific polymer are deteriorated, so that the electrode resistance is increased and the charge and discharge characteristics are deteriorated over time. In view of these, the content ratio of the structural unit (E) in the specific polymer is preferably 75% by mass or less, more preferably 40 to 60% by mass, based on the entire structural unit. The content ratio of the structural unit (F) in the specific polymer is preferably 10% by mass or less in all the structural units. By setting the ratio in the range, deterioration of ion conductivity or deterioration of adhesion accompanying introduction of structural units (C), (D), and (E) can be suppressed. When the electrode binder composition of the present invention is used for the electrode of the positive electrode or the capacitor, the specific polymer contained in the composition has the structural unit (A) and the structural unit (B) and the structural unit (C) and the structural unit ( D), and the content ratio is in all structural units, preferably as follows: Structural unit (A): 10 to 50% by mass, preferably 15 to 40% by mass. Structural unit (B): 5 to 30% by mass Preferably, it is 10 to 30% by mass. 201209116 Total of structural unit (A) and structural unit (B): 20 to 60% by mass, preferably 25 to 50% by mass. Structural unit (C): 2 to 5 mass% Unit (D): 30 to 75 mass%, preferably 3 5 to 60 mass% The specific polymer contained in the electrode binder composition for the electrode of the positive electrode or the capacitor is preferably a structural unit (E) The content ratio of the structural unit (F) is 5% by mass or less in all the structural units, and preferably does not include any of the structural unit (E) and the structural unit (F). When the electrode binder composition of the present invention is used in a negative electrode, the specific polymer contained in the composition preferably has a structural unit (A) and a structural unit (B), and a structural unit (C) and a structural unit (E). The content ratio is preferably as follows in all the structural units: Structural unit (A): 10 to 50% by mass, preferably 15 to 40% by mass. Structural unit (B): 5 to 30% by mass, preferably 10 to 30% by mass The total of the structural unit (A) and the structural unit (B): 20 to 60% by mass, preferably 25 to 50% by mass. Structural unit (C): 2 to 5 mass%. Structural unit (E) 45 to 55 mass% The specific polymer contained in the electrode binder composition used for the electrode in the negative electrode is preferably such that the structural unit (D) and the structural unit (F) are contained in all structural units. It is 5% by mass or less, and preferably does not contain any of the structural unit (D) and the structural unit (F). -15-201209116 [Manufacturing method of specific polymer] A specific polymer can be produced by polymerizing a mixture of monomers as described above. The polymerization method of the monomer mixture is not particularly limited, but an emulsion polymerization method is preferably used. When a specific polymer is obtained by an emulsion polymerization method, an emulsifier, a polymerization initiator, a molecular weight modifier or the like can be suitably used. These emulsifiers may be used singly or in combination of two or more kinds of anionic surfactants, nonionic surfactants, amphoteric surfactants, and the like. Specific examples of the anionic surfactant include, for example, a sulfate of a higher alcohol, an alkylbenzenesulfonate, an aliphatic sulfonate, a sulfated vinegar of a polyethylene glycol base, and the like; a nonionic surfactant; Specific examples thereof include an alkyl ester of polyethylene glycol, an alkyl ether of polyethylene glycol, and an alkylphenyl ether of polyethylene glycol. As the amphoteric surfactant, an anion moiety may be a carboxylate, a sulfate salt, a sulfonate or a phosphate salt, and a cationic moiety may be an amine salt or a quaternary ammonium salt. Specific examples of the amphoteric surfactant include, for example, betaines such as lauryl betaine and stearyl betaine; lauryl-/3-aniline, lauryl bis(aminoethyl)glycine, and octyl A surfactant such as an amino acid such as a bis(aminoethyl)glycine or the like. The emulsifier is preferably used in a proportion of 1 〇〇 by mass based on the total of the monomers used. 5 to 5 parts by mass. Specific examples of the polymerization initiator include water-soluble polymerization initiators such as sodium persulfate, potassium persulfate, and ammonium persulfate; benzamidine peroxide, lauryl peroxide, and 2,2'-azo. An oil-soluble polymerization initiator such as diisobutyronitrile; a redox polymerization initiator which is a combination of a reducing agent such as sodium hydrogen sulfite and the like. These polymerization initiators may be used alone or in combination of two or more. The use ratio of the polymerization initiator is preferably 10,000 parts by mass based on the total of the monomers used. 3 to 3 parts by mass. Specific examples of the molecular weight modifier include halogenated hydrocarbons such as chloroform and carbon tetrachloride; n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, and thirteen-dodecyl mercaptan. Thiol derivatives such as thioglycolic acid; xanthogen derivatives such as dimethylxanthogen disulfide and diisopropylxanthogen disulfide; other molecular weights such as terpinolene and methylstyrene dimer Conditioner. The use ratio of the molecular weight modifier is preferably 5 parts by mass or less based on the total of the monomers used. The emulsion polymerization is preferably carried out in a suitable aqueous medium, preferably in water. The total content of the monomers in the aqueous medium may be 10 to 50% by weight, preferably 20 to 40% by weight. The conditions of the emulsion polymerization are not particularly limited, and for example, it can be carried out at a polymerization temperature of 40 to 85 ° C and a polymerization time of 2 to 16 hours. The best emulsion polymerization method is as follows. That is, in an aqueous medium containing at least a polymerization initiator, emulsion polymerization is started by adding an emulsion of a monomer mixture (hereinafter referred to as "monomer emulsion") and, if necessary, addition of a monomer emulsion Knot -17- 201209116 The method of continuing the polymerization after the bundle. The temperature of the aqueous medium containing the above polymerization initiator is preferably from 40 to 85 ° C, more preferably from 60 to 80 ° C. In this case, in order to avoid decomposition of the polymerization initiator during the temperature increase, it is preferred to add a polymerization initiator to the polymerization medium after the temperature of the aqueous medium is raised to some extent (for example, after 40 to 70 ° C). After the agent has not been added for a long period of time, the addition of the monomer emulsion is started. The aqueous medium containing the polymerization initiator may further contain any component such as the above molecular weight regulator. The monomer emulsion can be adjusted by adding the monomer and the emulsifier and optionally any other components to the aqueous medium, and adjusting the content of the monomer in the emulsion to be 40 to 80. The weight % is more preferably 50 to 70% by weight. The addition of the monomer emulsion to the aqueous medium containing the polymerization initiator is preferably carried out so that the polymerization initiator is not localized in the reaction liquid and does not cause uneven polymerization. The addition time is preferably 0. 5 to 6 hours, preferably 1 to 4 hours. After the addition of the monomer emulsion is completed, the polymerization is preferably continued. The temperature at which the polymerization is continued in this case is preferably from 40 to 85 ° C, more preferably from 60 to 80 ° C. The time to continue the aggregation is better. 5 to 6 hours, preferably 1 to 4 hours. The total polymerization time from the start of the addition of the monomer emulsion is preferably from 1 to 12 hours, more preferably from 3 to 8 hours. [Characteristics of Specific Polymer] The glass transition temperature (Tg) of the specific polymer contained in the binder composition for an electrode of the present invention is preferably -45 to 25 °C. The glass transition temperature (Tg) of a particular polymer can be determined as follows. About 4 g of the latex in which the specific polymer was dispersed was poured into a Teflon (registered trademark) disk of 5 cm x 4 cm at 70 °C. The film was dried in a thermostat for 24 hours to form a film having a film thickness of about 100. About 10 mg of the sample was cut out from the obtained film, which was collected into an aluminum container and sealed. Next, using a differential scanning calorimeter (manufactured by NETZSCH-GerStebau GmbH, type "DSC204F1"), the differential scanning calorimetry was carried out in a temperature range of -80 ° C to 100 ° C at a temperature increase rate of 20 ° C / min in an air atmosphere. The glass transition temperature Tg was determined based on the obtained DSC chart. When the glass transition temperature (Tg) was determined from the DSC chart, it was carried out in accordance with the glass transition temperature at the intermediate point described in JIS K7121. (Liquid Medium) The electrode binder composition of the present invention contains the specific polymer as described above and a liquid medium. The liquid medium may be an aqueous medium or a non-aqueous medium. The electrode binder composition of the present invention is preferably a slurry or a latex obtained by dispersing the above specific polymer in an aqueous medium, or a solution in which a specific polymer is dissolved in a nonaqueous medium. The above aqueous medium contains water. The aqueous medium may contain a small amount of non-aqueous medium other than water. The non-aqueous medium may, for example, be a guanamine compound, a hydrocarbon, an alcohol, a ketone, an ester, an amine compound, a lactone, an anthracene or an anthracene compound, and one or more selected from the above may be used. The content ratio of the non-aqueous medium is preferably ι〇% by mass or less, more preferably 5% by mass or less, and the aqueous medium preferably contains no non-aqueous medium and is composed only of water, with respect to -19 - 201209116. . The specific polymer is preferably particulate in an aqueous medium. The number average particle diameter of the specific polymer in the aqueous medium is preferably from 50 to 190 nm, more preferably from 70 to 185 nm. By causing the number average particle diameter of the specific polymer to fall within the above range, the migration of the polymer particles does not occur in the drying step in forming the electrode active material layer, and the composition of the electrode active material layer thus obtained becomes uniform As a result, a sufficient number of effective adhesion points are obtained between the electrode active material and the polymer particles and the current collector, so that high adhesion can be obtained. The number average particle diameter of a specific polymer can be determined by using a laser particle size analysis system "LPA-3 000S/3 100" manufactured by Otsuka Electronics Co., Ltd., using water as a dispersion medium, and measuring by dynamic light scattering. The diameter is calculated as the number average 値. On the other hand, the above non-aqueous medium can be suitably used as long as it can dissolve a specific polymer. Specific examples of the non-aqueous medium include, for example, an aliphatic hydrocarbon such as Zhengxinyuan, Yixinyuan, Shuyuan, guanidine, decalin, pinene, and chlorododecane; cyclopentane and cyclohexane. a cyclic aliphatic hydrocarbon such as cycloheptane or methylcyclopentane; an aromatic hydrocarbon such as chlorobenzene, chlorotoluene, ethylbenzene, diisopropylbenzene or cumene; methanol, ethanol, propanol or isopropanol Alcohols such as butanol, benzyl alcohol, glycerol; (S> -20- 201209116 ketones such as acetone, methyl ethyl ketone, cyclopentanone, isophorone; methyl ethyl ether 'diethyl acid, Acids such as tetrahydrofuran, dioxane, and other lactones; lactones such as r-butyrolactone and 5-butyrolactone; and indoleamines such as /3-indoleamine; dimethylformamide, N-methyl A chain or cyclic guanamine compound such as pyrrolidone or dimethylacetamide; methylene cyanohydrin, ethylene cyanohydrin, 3,3'-thiodipropionitrile, acetonitrile, etc. a nitrile-based compound; a nitrogen-containing heterocyclic compound such as pyridine or pyrrole; a glycol compound such as ethylene glycol or propylene glycol; diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol ethyl butyl ether, etc. Ethylene glycol or a derivative; ethyl formate, ethyl lactate, propyl lactate, methyl benzoate, methyl acetate, methyl acrylate, etc., etc. The specific polymer in the binder composition for an electrode of the present invention The content ratio is preferably from 20 to 60% by mass, more preferably from 25 to 50% by mass. (Tackifier) The above-mentioned tackifier may be contained in the electrode binder composition of the present invention for further improving electrode bonding. The coating composition, charge and discharge characteristics, etc. of the composition of the agent. Examples of the tackifier include cellulose derivatives such as carboxymethyl cellulose, methyl cellulose, and hydroxypropyl cellulose; and polyacrylic acid such as sodium polyacrylate. Salt, etc., and -21 - 201209116 polyvinyl alcohol, polyethylene oxide, polyvinyl pyrrolidone, (meth)acrylic acid-vinyl alcohol copolymer, maleic acid-vinyl alcohol copolymer, modified polyvinyl alcohol, poly Ethylene glycol, ethylene-vinyl alcohol copolymer, polyvinyl acetate partial saponified product, etc. The amount of the tackifier in the electrode binder composition of the present invention is relative to the total solid content of the electrode binder composition. (liquid in the composition) The total mass of components other than the mass) is preferably 20 wt% or less, more preferably 0. 1 to 10% by weight. (Preferred state of the electrode binder composition) The electrode binder composition of the present invention is preferably a latex in which a specific polymer is dispersed in an aqueous medium in the form of particles. The electrode composition for an electrode of the present invention is preferably used by directly synthesizing (polymerizing) a polymerization reaction mixture such as the above-mentioned specific polymer in an aqueous medium as needed, and then directly using it. Accordingly, the electrode binder composition of the present invention may contain an emulsifier, a polymerization initiator or a residue thereof, a surfactant, a neutralizing agent, and the like in addition to the polymer particles and the aqueous medium. The content ratio of the other components is preferably 3% by weight or less, more preferably 2% by weight or less based on the total weight of the other components based on the total solid content of the component. The component concentration (the ratio of the total mass of the components other than the liquid medium in the composition to the total mass of the composition) is preferably from 20 to 60% by weight, more preferably from 25 to 50% by weight. As for the liquidity of the electrode binder composition, it is preferably in the vicinity of neutrality (S> -22- 201209116 is more preferably ρΗ6·0~8. 5, preferably ρ Η 7 · 0 ~ 8 can use the well-known water-soluble acid or alkali. As for the nitric acid, sulfuric acid, phosphoric acid, etc.; the base can be exemplified by potassium, lithium hydroxide, ammonia, and the like. The electrode binder composition of the present invention contains a polymer of a structural unit (Β). Therefore, it is understood that a high adhesion, an electrical conductivity, and an electrochemical safety device in a high temperature environment can be obtained. <Slurry for Electrode> The slurry for an electrode of the present invention contains an electrode active electrode composition for an electrode of the present invention. The polar active material and the electrode for use in the present invention contain other components as needed. (Electrode Active Material) The electrode active material can be selected according to the purpose of electrification. In the electrode binder composition of the present invention, the electrode for the positive electrode of the battery is used. (The positive electrode active material) may be an electrode of the present invention such as cobalt lithium, lithium iron phosphate or ternary nickel cobalt cobalt manganate. Using a binder composition to make . Hey. For example, hydrochloric acid, for example, sodium hydroxide or hydrogen hydroxide, has a structural unit (Α, an electrochemical substance which is excellent in both of the examples described later in a low-temperature environment, and The electrode active lithium acid, lithium nickelate, and barium manganate are used for the purpose of forming a lithium ion paste when the type of the device is appropriately used, such as the slurry degreaser composition for the electrode described above. In the case of forming a slurry for a negative electrode of a lithium ion -23-201209116 battery (a slurry for a negative electrode), for example, a carbon material, carbon, or the like can be used as the electrode active material (negative electrode active material). The carbon material can be exemplified by a carbon material obtained by firing an organic polymer compound, coke, or pitch, and the organic polymer compound of the carbon material precursor is exemplified by, for example, a phenol resin, polyacrylonitrile, or cellulose. The above carbon may, for example, be artificial graphite, natural graphite or the like. When the electrode binder composition of the present invention is used for forming an electrode slurry for an electrode for an electric double layer capacitor, for example, graphite, non-graphitizable carbon, or hard carbon can be used as the electrode active material; coke, asphalt, etc. A carbon material obtained by firing; a polyacene organic semiconductor (PAS) or the like. (Other components) The slurry for an electrode of the present invention may further contain a tackifier, a dispersing agent, a surfactant, an antifoaming agent or the like as needed. The tackifier may be the same as the above-mentioned exemplified as the tackifier which may be optionally contained in the electrode binder composition of the present invention. Examples of the dispersant include sodium hexametaphosphate, sodium tripolyphosphate, and polycondensation. Sodium acrylate or the like; the above surfactant may, for example, be a nonionic surfactant or an anionic surfactant as a stabilizer for a latex. The content ratio of the other components is preferably 1% by weight or less, more preferably 1% by weight or less, based on the total solid content of the slurry for an electrode of the present invention (the total mass of components other than the liquid medium in the composition). 0. 5 to 5 wt% (§> -24-201209116 (best aspect of the slurry for electrodes) The slurry for electrodes is 100 parts by mass based on the electrode active material, and the electrode binder composition is calculated in terms of solid content. Good contains 0. 1~10 parts by mass, more preferably 0. 3 to 4 parts by mass. By the ratio of the content of the electrode binder composition, it is 0 in terms of solid content. 1 to 10 parts by mass makes it difficult to dissolve a specific polymer in an electrolytic solution used in an electrochemical device, and as a result, it is possible to suppress adverse effects on device characteristics due to an increase in overvoltage. The slurry for electrodes is prepared by mixing the electrode binder composition of the present invention, the above-mentioned electrode active material, and other components as needed. A means for mixing these may be a conventional mixing device such as a stirrer, a defoaming machine, a bead honing machine, a high pressure homogenizer or the like. The preparation of the electrode slurry is preferably carried out under reduced pressure, whereby generation of bubbles in the electrode active material layer can be prevented. The electrode slurry can be formed by containing the electrode binder composition of the present invention. An electrode active material layer having high adhesion between the electrode active materials and the electrode active material and the current collector, and an electrochemical property excellent in both the discharge rate in a low-temperature environment and the electrochemical stability in a high-temperature environment. Learning device. <Electrode> The electrode of the present invention includes: a current collector, -25-201209116 An electrode active material layer formed by applying the above-described electrode slurry to the surface of the current collector and drying it. After the coating film is dried, it is preferably subjected to press working. (Collector) As the current collector, for example, a metal foil, an etched metal foil, an expanded metal or the like can be used. Specific examples of such materials include metals such as aluminum, copper, nickel, ruthenium, stainless steel, and titanium, which can be appropriately selected depending on the type of electrochemical device to be used. For example, when a positive electrode of a lithium ion secondary battery is formed, the above-mentioned aluminum is preferably used as the current collector. In this case, the thickness of the current collector is preferably 5 to 3, more preferably 8 to 2 5 // m. On the other hand, when forming a negative electrode of a lithium ion secondary battery, it is preferable to use the above-mentioned copper as a current collector. In this case, the thickness of the current collector is preferably 5 to 30 #m, more preferably 8 to 25/m. Further, when forming an electrode for an electric double layer capacitor, it is preferable to use aluminum or copper as the current collector. In this case, the thickness of the current collector is preferably 5 to 1 Å/zm, more preferably 10 to 70/m, and most preferably 15 to 30/m. (Formation of Electrode Active Material Layer) The electrode active material layer in the electrode is formed by a step of applying a slurry for an electrode on the surface of the current collector as described above and drying it. For the method of applying the slurry for an electrode to the current collector, for example, a method such as a doctor blade coating method, a reverse roll method, a Koma coating, a gravure printing method, or an air knife method can be used, and a method suitable from -26 to 201209116 can be used. The drying treatment of the coating film is preferably from 20 to 2 50. (:, preferably in the temperature range of 50 to 150 ° C, preferably 1 to 120 minutes, more preferably 5 to 60 minutes. The film after drying is preferably used for pressing processing. For example, a roll press, a high pressure super press, a soft calender, a 1 ton press, etc. The press processing conditions are suitably set depending on the type of the machine to be used and the thickness and density required for the electrode active material layer. The layer is preferably 40 to 100/zm thick. Density 1·3~2·0 g/cm3. (Features of the electrode) The electrode formed as described above is formed by using an electrode slurry containing the binder composition of the present invention, and thus the electrode active material in the electrode active material layer and the electrode activity The substance-collective body is highly dense. Further, when the electrode is used, an electrochemical device which is excellent in both the discharge rate characteristics in a low temperature environment and the electrochemical stability in a high temperature environment can be obtained. The electrode of the present invention can be suitably used as an electrode of an electrochemical device such as a lithium ion secondary battery, an electric double layer capacitor, or a lithium ion capacitor. When a battery such as a lithium ion battery is used, an electrode formed using the binder composition of the present invention can be used as a positive electrode or a negative electrode, and exhibits performance superior to those of the prior art, as understood from the examples described later, when used as a positive electrode It is preferred from the standpoint of achieving higher effects. -27-201209116 <Electrochemical device> The electrochemical device of the present invention comprises the electrode as described above. The electrochemical device of the present invention has a structure in which the electrode permeating electrolyte as described above is opposed to the counter electrode, and is preferably isolated by the presence of the separator. The manufacturing method is exemplified by, for example, superposing two electrodes (two positive electrodes and two negative electrodes or two electrodes for capacitance) through a separator, and winding and folding them into a battery container or the like, and placing them in a battery container. A method of injecting an electrolyte into a container and sealing it. The shape of the battery may be a coin shape, a button type, a sheet type, a cylinder type, a square type, a flat type, or the like. The above electrolyte solution may be appropriately selected depending on the type of electrochemical device to be used. As the electrolytic solution, a solution obtained by dissolving an appropriate electrolyte in a solvent is used. When a lithium ion secondary battery is fabricated, a lithium compound is used as the electrolyte. Specific examples thereof include LiC104, LiBF4, Lil, LiPF6, L1CF3SO3, LiAsF6, LiSbF6, L1AICI4, LiCl, LiBr, LiB(C2H5)4, L1CH3SO3'L1C4F9SO3, Li(CF3S02)2N, and the like. The electrolyte concentration in this case is preferably 0. 5~3. 0 mole / L, better 0. 7~2. 0 mole / L. When an electric double layer capacitor is produced, for example, tetraethylammonium tetrafluoroborate, triethylmethylammonium tetrafluoroborate, tetraethylammonium hexafluorosulfate or the like is used as the electrolyte. The electrolyte concentration in this case is preferably 〇. 5~3. 〇莫耳/L, better 0. 7~2. 0 mole / L. The type and concentration of the electrolyte in the manufacture of a lithium ion capacitor are the same as those in the lithium ion storage -28-201209116 battery. In any of the above cases, the solvent used in the electrolytic solution may, for example, be a carbonate such as propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate or methyl carbonate; a lactone such as butyrolactone; an ether such as trimethoxydecane, iota, dimethoxyethane, diethyl ether, 2-ethoxyethane, tetrahydrofuran or 2-methyltetrahydrofuran; a sulfonium derivative such as methyl hydrazine; an oxolane derivative such as 1,3-dioxolane or 4-methyl-1,3-dioxolane; acetonitrile, nitromethane, etc. Nitrogen-containing compound; methyl formate, methyl acetate, butyl acetate, methyl propionate, ethyl propionate, phosphate triester, etc.; diethylene glycol dimethyl ether, triethylene glycol dimethyl ether (triglyme Ethylene glycol dimethyl ether compound such as tetraethylene glycol dimethyl ether; ketones such as acetone, diethyl ketone, methyl ethyl ketone or methyl isobutyl ketone » oxime compound such as cyclobutyrene; An oxazolidinone derivative such as methyl-2-oxazolidinone; 1,3-propane sultone, 1,4-butane sultone, 2,4-butane sultone, 1: Sulfonactone such as 8-naphthalene lactone Thereof and the like. The electrode active materials in the electrode active material layer of the electrochemical device have high adhesion to the electrode active material-collector, and the discharge rate characteristics in a low temperature environment and the electrochemical environment in a high temperature environment Stability -29- 201209116 Both are excellent. According to this, the electrochemical device can be used as a battery or a capacitor used in an AV device, an OA device, a communication device, or the like, in addition to a battery or a capacitor mounted on an automobile such as an electric vehicle, a hybrid electric vehicle, or a truck. EXAMPLES Hereinafter, the present invention will be specifically described by way of examples and comparative examples. However, the invention is not limited to the embodiments. The "parts" in the following examples and comparative examples are based on mass unless otherwise specified. The evaluation methods of the electrode and the electrochemical device in the following examples and comparative examples are as follows. <Evaluation of Electrode> (1) Peel strength of electrode active material layer A test piece having a width of 2 cm X and a length of 12 cm was cut out from the electrode (laminate). The surface of the test piece on the electrode active material layer side was bonded to an aluminum plate with a double-sided tape. A tape having a width of 18 mm (JIS Z 1 522 standard product, trade name "Cellotape (registered trademark)", manufactured by Nichiban Co., Ltd.) was attached to the surface of the current collector side of the test piece on the aluminum plate. While maintaining the angle of the aluminum plate at 90°, the tape was pulled up at a speed of 50 mm/min upward, and the peel strength (mN/km) at a peeling angle of 90° was measured 6 times, and the average 値 was calculated as Peel strength (mN/2cm) of the electrode active material layer. Further, "mN/2cm" is a unit indicating the peel strength of 毎 201209116 2 cm. The higher the peel strength, the higher the adhesion strength between the current collector and the electrode active material layer, and it can be judged that it is difficult to peel off the electrode active material layer from the current collector. In particular, the crucible is good when it is 90 mN/2 cm or more. <Evaluation of Lithium Ion Battery> (1) Low temperature rate characteristics (3. 0C/0. 2C) First, make the lithium ion battery at -2 (TC with constant current (0. 2C) · Constant voltage (3. 8V) way to charge, with constant current (0. 2C) The discharge is a cycle, and the discharge capacitance after repeated 3 cycles is determined (CQ. 2 ). Next, the battery was measured at -20 ° C with a constant current (0. 2C). Constant voltage (3. 8V) way to charge, to constant current (3. 0C) The discharge capacitance when discharging (C 3. 〇). Using this measurement, the low temperature rate characteristic of the lithium ion secondary battery was calculated by the following formula (3. 0C/0. 2C) ( % ). Low temperature rate characteristic (%) = {(C3. 〇) + (C〇. 2)} X 1 0 0 The higher the temperature-lowering characteristic, the smaller the change in electrode characteristics in a low-temperature environment. In particular, it is good when the enthalpy is 80% or more. Further, "1 C" in the measurement conditions means that the battery having a certain capacitance is discharged at a constant current for one hour to become a discharge current. For example, "0. 1C" means the current that becomes the end of discharge after 10 hours, 10C means 0. One hour becomes the current at the end of the discharge. (2) Self-discharge rate in high temperature environment -31 - 201209116 First, determine the constant current (0-2C) of the lithium ion battery at normal temperature (25 °C). 8V) way to charge, to constant current (0. 2C) The discharge capacitance at the time of discharge (C. Next, the measurement is made to make the battery constant current at normal temperature (25 ° C) (0. 2C). Constant voltage (3. 8V) charging, after standing at 85 ° C for 3 days, has been cooled to normal temperature (25 ° C) after constant current (0. 2C) The discharge capacitance (C:^) at the time of discharge. Using these measurement enthalpies, the self-discharge rate (%) was calculated from the following formula. Self-discharge rate (%) = [{(C before) (after C)} + (before C)] X100 The self-discharge rate is smaller, and it can be judged that the self-discharge in a high temperature environment can be suppressed. In particular, it is good when the enthalpy is less than 30%. (3) Cyclic characteristics Make the lithium ion battery with constant current (0_2C). Constant voltage (3. 8V) way to charge, to constant current (0. The method of 2C) discharges into one cycle and repeats 5 times. The discharge capacity (C3 (fiiB) of the third cycle and the discharge capacitance (C 5〇_) of the 50th cycle were measured, and the cycle characteristics (%) were calculated from the following equation. Cycle characteristics (%) = {(C50 cycle) + (C3 cycle)} XI 00 This cycle characteristic is close to 100%, and it can be judged that deterioration of battery characteristics due to oxidative decomposition of the binder due to charge and discharge can be suppressed, especially when the enthalpy is 80% or more. <Evaluation of electric double-layer capacitors> (1) Self-discharge rate (%) under high temperature environment The electric double-layer capacitor is rated at a constant temperature (25 ° C) at a constant current ( -32 - 201209116 1 OmA / F ). Constant voltage (2. 5V) The voltage after charging for 1 hour (V Zhao). Next, the voltage (Vta) of the electric double layer capacitor after leaving it at 85 ° C for 3 days was measured. Using these measurement enthalpies, the self-discharge rate (%) was calculated from the following formula. Self-discharge rate (8) = [{(V before) - (after V)} + (before V)] X10 0 The above self-discharge rate is smaller, and it can be judged that the self-discharge in a high temperature environment can be suppressed. Especially when the cockroach is less than 30%, it is good. (2) Cyclic characteristics Make the electric double layer capacitor with constant current (1C) · constant voltage (3. 5V) is charged in the manner of discharging at a constant current (1C) for one cycle and repeating 100 cycles. At this time, the discharge capacity (C3_) of the third cycle and the discharge capacity (Cnwes) of the first cycle were measured, and the cycle characteristics (%) were calculated from the following formula. Cycle characteristics (%) = {(C100 cycles) + (C3 cycles)} χιοο The cycle characteristics are close to 100%, and it can be judged that the deterioration of battery characteristics caused by oxidative decomposition of the binder due to charge and discharge can be suppressed. . Especially when the 値 is 80% or more, it is good. <Preparation Example of Electrode Composition for Electrode> Example 1 150 parts of water and sodium dodecylbenzenesulfonate 0. Two parts were fed into a separable flask having a capacity of 7 liters, and the inside of the separable flask was sufficiently replaced with nitrogen. On the other hand, 60 parts of water was added to another container, and the conversion solid was -33-201209116 divided into 0. 8 parts of an ether sulfate type emulsifier as an emulsifier (trade name "ADEKA REASOAP SR 1 025", manufactured by ADEKA Co., Ltd.), and 2,2,2-trifluoroethyl methacrylate as a monomer Parts, 25 parts of acrylonitrile, 10 parts of methyl methacrylate, 40 parts of 2-ethylhexyl methacrylate, and 5 parts of methacrylic acid, and sufficiently stirred to prepare a monomer emulsion containing the above monomer mixture. Subsequently, the inside of the separable flask was started to be heated, and when the internal temperature of the separable flask reached 60 ° C, ammonium persulfate as a polymerization initiator was added. 5 servings. Next, when the internal temperature of the separable flask reaches 70 ° C, the monomer emulsion prepared above is added, the internal temperature of the separable flask is maintained at 70 ° C, and the monomer emulsification is slowly added within 3 hours. liquid. Subsequently, the internal temperature of the separable flask was raised to 85 ° C, and the polymerization was carried out at this temperature for 3 hours. After 3 hours, the separable flask was cooled and the reaction was terminated, and the pH was adjusted to 7. 6. Modulate the electrode composition (s 1 ). The solid electrode concentration of the obtained electrode binder composition (s 1 ) was 30% by mass. The polymer in the electrode binder composition (si) was in the form of particles having a glass transition temperature of -10 ° C and a number average particle diameter of 100 nm. Examples 2 to 6 and Comparative Examples 1 to 5 and 7 were prepared in the same manner as in Example 1 except that the monomer was used in the same manner as shown in the following Table 1, and the electrode binder composition (s2) was prepared. (s6) and (r1)~(r5) and (r7). The glass transition temperature (S) -34 - 201209116 degrees of the polymer in the adhesive composition of each electrode obtained and the number average particle diameter of the polymer particles are listed in Table 1 below. <(Example 7 150 parts of water and sodium dodecylbenzenesulfonate. 2 parts were fed into a separable flask having a capacity of 7 liters, and the inside of the separable flask was sufficiently replaced with nitrogen. On the other hand, another 60 parts of water was added to the container, and an ether sulfate type emulsifier (trade name "ADEKA REASOAP SR 1 025", manufactured by ADEKA Co., Ltd.) and methacrylic acid as a monomer were added as an emulsifier in a solid content of 0.8 parts. 25 parts of 2,2,2-trifluoroethyl ester, 25 parts of acrylonitrile, 10 parts of methyl methacrylate, 40 parts of 2-ethylhexyl methacrylate and 5 parts of methacrylic acid, and prepared by thorough stirring a monomer emulsion containing the monomer mixture. After the total amount of the monomer emulsion is added to the separable flask, the temperature is raised, and the internal temperature of the separable flask reaches 6 (TC), and the addition is as a polymerization. 0.5 parts of ammonium persulfate as a starting agent. Then, the internal temperature of the separable flask was raised to 70 t, and after maintaining the temperature for 3 hours, the temperature was raised to 85 ° C for polymerization for 3 hours. Subsequently, the separable flask was separated. After cooling and stopping the reaction, add ammonia to the pH. Adjusted to 7.6, the electrode composition for the electrode is s7. The solid content of the electrode binder composition (s7) is 30% by mass. The polymer in the electrode binder composition (s7) is glass transfer. The temperature system was _丨ot, and the number average particle diameter was 100 nm. Comparative Example 6 - 35 - 201209116 The same procedure as in the above Example 7 was carried out except that the monomer was used in the formulation shown in Table 1 below. The binder composition (r6). The glass transition temperature of the polymer in the obtained binder composition (r6) and the number average particle diameter of the polymer particles are listed together in Table 1 below. Example 8 Temperature with a stirrer In an adjustable autoclave, 200 parts of water, 〇6 parts of sodium dodecylbenzenesulfonate, 1.0 part of potassium persulfate and 5 parts of sodium hydrogen sulfite, and methacrylic acid as a monomer are fed in one time. 25 parts of 2,2-trifluoroethyl ester, 25 parts of acrylonitrile, 16 parts of styrene, 35 parts of butadiene, and 4 parts of methacrylic acid were subjected to polymerization at 80 ° C for 6 hours to obtain a polymer dispersion. Subsequently, an aqueous ammonia solution is added to the obtained polymer dispersion to adjust the pH. After the addition of 7.4, sodium acrylate as a tackifier was added, and the residual monomer was removed by steam distillation, and then the solid content concentration was concentrated to 48% by mass under reduced pressure, thereby modulating electrode bonding. Agent Composition (s8) » The glass transition temperature of the polymer in the obtained electrode binder composition (s 8 ) and the number average particle diameter of the polymer particles are listed together in Table 1 below. Comparative Example 8 In accordance with Table 1 below The blending treatment shown is carried out in the same manner as in the above-mentioned Example 8 except that the monomer is transferred, and the binder composition (r8) for the electrode is prepared. The glass transition temperature and polymerization of the polymer in the obtained electrode binder composition (r8) are obtained. The number average particle diameter of the particles is shown in Table 1 below. -36- 201209116 丽·Ν%ι^ίi Example 8 1 CO (/> 〇〇CM o LO CM JO ο ο CO ιο C0 ο 〇σ>σ> Example 7 υ υ > S 〇. in eg o Ir> CM tn ΙΟ ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο m ο ο ο ο ο ο 实施 实施 实施 实施 Λ in in in in in in in in in in in in in in in in in in in in in in in in in in in in in in in in in in in in in in in in in in in in in in in in in in in in in AS in AS AS in in in AS in in in in in AS O in m tn ο ο ο ο ο ο S 实施 2 CM (0 〇〇 ooos lO tn eg S ο ο ο ΙΟ S τ*~ Example 1: 〇〇s in CM o lO CM § in Ο ο ο ο ο ο C0 σ> I Binder Composition Name 2,2,2-Trifluoroethyl methacrylate t 2,2,2-Trifluoroethyl acrylate 1,1,1,3,3,3- Hexafluoroisopropyl vinegar structural unit (A) content ratio Acrylonitrile methacrylonitrile structural unit (B) content ratio structural unit (A) + structural unit (B) methyl methacrylate methyl methacrylate 2-ethylhexyl acrylate styrene butadiene ethylene glycol dimethyl propylene Glass transition temperature of ester 1 polymer (°c) 1 Number average particle size of polymer particles (ηπι) s 2* Q Other (Qing Yi I) -37- 201209116 8 Li N Xia capsule - s Comparative Example 8 1 00 m 〇〇m 〇o ο in 卜 in 〇CO CO 5 〇〇g Comparative Example 7 卜ο 〇〇〇mo in in if> ο S 〇〇〇§ 1 ο Comparative Example 6 CO s 〇〇〇o ο s ο 〇〇C0 00 C0 ο Comparative Example 5 in 8 〇〇〇o ο sm ο 〇〇 〇〇 CO 1〇C0 1 s Comparative Example 4 inch CM in 〇〇CM ΙΟ ιο CM o in CO ο 8 〇〇〇ο Compare Example 3 CO LO CD 〇〇ΙΟ (D LO o in o CO ο 〇〇〇m CO Comparative Example 2 CM o 〇〇Ο 9 o CM it> in ο 〇〇〇CM s Comparative Example 1 CO 〇〇CO CO o CO to m ιη CM S 〇〇〇in CVJ s Composition name I methacrylic acid 2,i2-trifluoroethyl acrylate 2,2,2-trifluoroethyl acrylate U,1,3,3,3-hexa Perfluoroisopropyl ester structural unit (Α) content ratio Acrylonitrile methacrylonitrile structural unit (B) content ratio structural unit (8) Adding unit (B) Methyl methacrylate methyl methacrylate Acid, 2-ethylhexyl acrylate styrene butadiene glycol dimethacrylate glass transition temperature (° c) 1 poly decorated particles of polymer of a number average particle diameter (nm) <Π m circle tfwml φΠΓ gs a Q Others (Dictionary) Di 锇翳 -1- 1- -38- 201209116 <Manufacture and evaluation of lithium ion battery (1), the electrode binder composition of the present invention is used in the positive electrode Examples 9 to 15 and Comparative Examples 9 to 1 5 The binder compositions (si) to (s7) and (rl) of the electrodes prepared in the above Examples 1 to 7 and Comparative Examples 1 to 7 were used. (Γ7), a lithium ion secondary battery was fabricated as follows and fF valence. (1) The positive electrode for lithium ion battery is manufactured by a biaxial type Banbury kneading machine (trade name "TK HIVIS MIX 2P-03", manufactured by PRIMIX Co., Ltd.), and a tackifier (trade name "CMC8 00H" is injected. (manufactured by DAICEL Chemical Industry Co., Ltd.), 1 part (converted solid content), 100 parts of lithium iron phosphate as a positive electrode active material (converted solid content), 5 parts of acetylene black as a conductive agent (converted solid content), and 70 parts of water, Stirring was carried out at 60 rpm for 1 hour. Subsequently, 2 parts of the electrode binder composition prepared in the above Examples and Comparative Examples (converted solid content) were added, and further stirred for 1 hour to obtain a paste. 90 parts of water was added to the obtained paste, and the solid content concentration was adjusted to 40% by mass, and then the mixture was stirred at 200 rpm for 2 minutes using a stirring defoaming machine (trade name "AWATORY", manufactured by THINKY Co., Ltd.). The slurry for the positive electrode was prepared by stirring at 1,800 rpm for 5 minutes and stirring and mixing for 1.5 minutes at 1,800 rpm under reduced pressure. Then, on the surface of the current collector made of aluminum foil having a thickness of 30/m, the film thickness of the coating film after drying was 90/zm, and the above-mentioned prepared positive electrode was coated by a doctor blade method. The slurry was dried at 120 ° C for 20 -39 - 201209116 minutes to obtain a coating film. Subsequently, press working was carried out using a roll press so that the density of the film became 1.7 g/cm 3 to form an electrode active material layer to form a laminate. A positive electrode for a disk-shaped lithium ion secondary battery having a diameter of 15.95 mm was produced by press working the laminate. The peeling strength of the electrode active material layer in the obtained positive electrode for each lithium ion secondary battery is shown in Table 2 below. (2) Production of a negative electrode for a lithium ion battery is carried out by injecting 4 parts of polyvinylidene fluoride (PVDF) into a biaxial type Banbury kneading machine (manufactured by PRIMIX Co., Ltd., trade name "TK HIVIS MIX 2P-03"). 100 parts of graphite (converted solid content) and 80 parts of N-methylpyrrolidone (NMP) as a negative electrode active material, and the mixture was stirred at 60 rpm for 1 hour. Subsequently, after 20 parts of NMP was further charged, it was stirred at 200 rpm for 2 minutes using a stirring deaerator (manufactured by THINKY Co., Ltd. under the trade name "AWATORY"), followed by stirring at 1,800 rpm for 5 minutes, and then subtracted. The mixture was stirred and mixed at 1,800 rpm for 1.5 minutes, and a slurry for a negative electrode was prepared. Then, on the surface of the current collector made of a copper foil having a thickness of 20 μm, the above-mentioned prepared negative electrode slurry was uniformly applied by a doctor blade method so that the film thickness after drying was 950 am. The material was dried at 120 ° C for 20 minutes to obtain a coating film. Subsequently, the film was processed using a roll press so that the density of the film became 1.8 g/cm 3 to form a laminate. The laminate was subjected to press working to produce a negative electrode for a disk-shaped lithium ion battery having a diameter of 16.16 mm. (S> -40- 201209116 (3) The lithium ion battery is manufactured in a glove box, and the lithium ion battery negative electrode is placed on a two-pole coin battery (trade name "HS flat cell", Baoquan ( On the negative electrode, a separator made of a porous film made of polypropylene (manufactured under the trade name "CELGARD #2400" 'CELGARD) was placed on the negative electrode, and then air was not used. Then, the electrolyte is injected in. The lithium ion battery is sealed by the outer casing of the lithium-ion battery after the positive electrode of the lithium ion battery is placed on the separator, and the lithium ion battery is used. A solution prepared by dissolving LiPF6 in a solvent having a concentration of 1 mol/L in a solvent of ethylene carbonate/ethyl carbonate = 1/1 (mass ratio). The low temperature rate characteristics of each lithium ion battery obtained, and the self in a high temperature environment The discharge rate and cycle characteristics are shown in Table 2. - 41 - 201209116 Example 15 〇s in s Example 14 CO (Λ C0 05 s CO CM in CO Example 13 LO (0 〇i σ> s eg m CO * Example 12 inch U) CM ay s ci in CO Example 11 C0 V) S s CM o Example 10 CM V) CO σ > Si lO CM σ > Example 9 (/> S a σϊ binder name | peel strength of electrode active material layer _/2 cm) I inclination rate 14 (%) | White line discharge rate in high temperature environment (%) Cycle characteristics (%) Comparative Example 15 | Bu 5 m ιο σ> CP Comparative Example 14 ο s Comparative Example 13 in s in CO Comparative Example 12 : S in in 00 Comparative Example 11 s ai Comparative Example 10 S s 5; Comparative Example 9 λ- S CO | Binder composition name I electrode active material layer peel strength (mN/2cm) | low temperature rate characteristic (% Self-discharge rate (%) in cycle temperature environment | cycle 14 (%) 42-201209116 From the results of Table 2, it is understood that the electrode composition (si) to (s7) of the electrode of the present invention is used to obtain an electrode. A positive electrode for a lithium ion secondary battery having a high peeling strength of the active material layer. Further, it has been confirmed that the lithium ion battery including such a positive electrode is excellent in both the discharge rate characteristics in a low temperature environment and the electrochemical stability in a high temperature environment. In particular, 2,2,2-trifluoroethyl methacrylate is used as the specific fluorine-containing (meth) acrylate, and acrylonitrile is used as the electrode binder composition (si) ~(s3) ' for the unsaturated nitrile compound. A positive electrode for a lithium ion secondary battery having a higher peeling strength of the electrode active material layer was obtained, and it was confirmed that a lithium ion secondary battery having excellent discharge rate characteristics in a low temperature environment and electrochemical stability in a high temperature environment was obtained. <Manufacture and Evaluation of Lithium Ion Battery (2), Examples of the Electrode Composition for Electrodes of the Present Invention Used in the Negative Electrode> Examples 16 to 18 and Comparative Examples 16 to 18 The above Examples 1, 7 and 8 and In the electrode compositions (si), (s7) and (s8) and (r5) to (r6) and (r8) prepared in Comparative Examples 5, 6 and 8, lithium ion batteries were produced and evaluated as follows. (1) Production of a negative electrode for a lithium ion battery In a biaxial type Banbury kneading machine (trade name "tk hi vis mix zp-cn", manufactured by PRIMIX), a tackifier is added (trade name "CMC22 00") 1 part (converted -43-201209116 solid content), 100 parts of graphite (converted solid content) and 68 parts of water as a negative electrode active material were stirred at 60 rpm for 1 hour. Then, one part (converted solid content) of each electrode binder composition prepared in the above Examples and Comparative Examples was added, and the mixture was further stirred for 1 hour to obtain a paste. After adding 34 parts of water to the obtained paste, the solid content concentration was adjusted to 50% by mass, and the mixture was stirred at 200 rpm for 2 minutes using a stirring defoaming machine (trade name "AWATORY", manufactured by THINKY Co., Ltd.). l, 800 rPm was stirred for 5 minutes, and further stirred at 1,800 rpm under reduced pressure for 1.5 minutes, thereby preparing a slurry for a negative electrode. Then, on the surface of the current collector made of a copper foil having a thickness of 20/zm, the prepared negative electrode slurry was uniformly applied by a doctor blade method so that the film thickness after drying was 80#m. The material was dried at 120 ° C for 20 minutes to obtain a coating film. Subsequently, the film was subjected to press working using a roll press to have a density of the film of 1.8 g/cm3 to form an electrode active material layer to form a laminate. The laminate was subjected to press working to produce a negative electrode for a disk-shaped lithium ion secondary battery having a diameter of 16.16 mm. The peeling strength of the electrode active material layer in the obtained negative electrode for each lithium ion secondary battery is shown in Table 3 below. (2) The positive electrode for lithium ion battery is manufactured in a biaxial type Banbury kneading machine (trade name "TK HI VIS MIX 2P-〇3", manufactured by PRIMIX), and 5 parts of polyvinylidene fluoride is added. Solid component), 100 parts of lithium iron phosphate as a positive electrode active material (converted solid content), and 5 parts of acetylene black as a conductive agent (converted solids (§> -44 - 201209116) and N-methylpyrrolidone (NMP) 25 parts of the mixture was stirred at 6 rpm for 1 hour. Then, 10 parts of NMP was added, and then stirred for 2 minutes at 20 rpm using a stirring deaerator (trade name "AWATORY", manufactured by THINKY Co., Ltd.). Then, the mixture was stirred at 1,800 rpm for 5 minutes, and further stirred and mixed at 1,800 rpm for 1.5 minutes under reduced pressure to prepare a slurry for the positive electrode. Next, on the surface of the current collector composed of aluminum foil having a thickness of 3 〇vm' The slurry for positive electrode prepared above was uniformly applied by a doctor blade method so that the film thickness after drying was 90 m, and dried at 12 (TC for 20 minutes to obtain a coating film. The density is 1.7 g/cm3, and the press is processed using a roll press. The electrode active material layer was formed into a laminate, and the laminate was subjected to press working to produce a positive electrode for a disk-shaped lithium ion battery having a diameter of 15.95 mm. (3) Manufacturing of a lithium ion battery, except that the negative electrode and the positive electrode manufactured above were used. A lithium ion secondary battery was produced and evaluated in the same manner as in the above Examples 9 to 15 and Comparative Examples 9 to 15. The evaluation results are shown in Table 3. -45 - 201209116 Comparative Example 18 | 00 CM 00 S CM CO CNJ CO Comparative Example 17 CO CO 00 σ > CO in CNJ Comparative Example 16 1 § CO CO a > CNJ s Example 18 〇〇V) σ > 7 CO 03 CsJ σ> Example 17 Bu V) g τ - § CO Example 16 ο in σ> in in σ> |Binder composition name 1 Peel strength of electrode active material layer (mN/2cm) Pour rate characteristic (%) Self-discharge rate in a temperature environment (%) Cycle characteristics ( %) i) -46- 201209116 As understood from the results of Table 3, when the electrode binder compositions (si), (s7) and (s8) of the present invention are used, the peeling strength of the electrode active material layer can be obtained. A negative electrode for a lithium ion battery. Therefore, the lithium ion secondary battery having such a negative electrode has been confirmed to have excellent discharge rate characteristics in a low temperature environment and electrochemical stability in a high temperature environment. However, when the adhesive composition for an electrode of the present invention is used in a positive electrode for a lithium ion secondary battery, the difference between the low temperature rate characteristic and the self-discharge rate in a high temperature environment is small between the examples and the comparative examples ( Refer to Table 2 above. From this, it is understood that the electrode composition for an electrode of the present invention can obtain a greater effect when it is used in a positive electrode. <Manufacture and Evaluation of Electric Double Layer Capacitor, Example of Electrode Composition for Electrode of the Present Invention Used in Capacitor Electrode> Examples 19 and 20 and Comparative Examples 19 to 21 (1) Fabrication of Electrode for Electric Double Layer Capacitor Activated carbon as an electrode active material in the biaxial type Banbury kneading machine (trade name "TK HI VIS MIX 2P-03", manufactured by PRIMIX Co., Ltd.) (trade name "KURARAY COAL YP"' KURARAY CHEMICAL )Manufactured) 6 parts, conductive carbon (trade name "DENKA BLACK", manufactured by DENKA Electrochemical Industry Co., Ltd.), 6 parts, tackifier (trade name "CMC2200", manufactured by DAICEL Chemical Industry Co., Ltd.) 2 The mixture and water 2W parts were stirred at 60 rpm for 1 hour. Then, 4 parts (in terms of solid content) of each of the electrode binder compositions produced in the above Examples and Comparative Examples were added and stirred for further 1 hour to obtain a paste. After adding 58 parts of water to the paste obtained in -47 - 201209116, the solid content concentration was adjusted to 25% by mass, and the mixture was stirred at 200 rpm using a stirring defoaming machine (trade name "AWATORY", manufactured by THINKY Co., Ltd.). After a minute, the mixture was stirred at 1,800 rpm for 5 minutes, and further stirred and mixed at 1,800 rpm for 1.5 minutes under reduced pressure to prepare a slurry for an electrode. Then, on the surface of the current collector made of aluminum foil having a thickness of 20 mm, the paste for positive electrode coating was uniformly applied by a doctor blade method so that the film thickness after drying was 150/μm. It was dried at 120 ° C for 20 minutes to obtain a coating film. Subsequently, press working was carried out using a roll press to form a film having a density of 1.5 g/cm 3 to form an electrode active material layer to form a laminate. The peeling strength of the electrode active material layer in the electrode for the electric double layer capacitor obtained by the electrode for the two types of disc-shaped electric double layer capacitors having a diameter of 15.59 mm and 16.16 mm by press working on the laminate is shown in the following table. 4. (2) Manufacturing and evaluation of electric double-layer capacitors In the glove box, electrodes for electric double-layer capacitors with a diameter of 16.16 mm are placed on a two-pole coin battery (trade name "HS flat battery", manufactured by Baoquan Co., Ltd.) )on. Then, a cellulose-based separator (trade name "TF4535", manufactured by NIPPON Kogyo Paper Co., Ltd.) having a disk diameter of 18 mm was placed on the electrode, and then the electrolyte was injected without allowing air to enter. Next, an electrode for an electric double-layer capacitor having a diameter of 15.95 mm was placed on the separator, and the electric double-layer capacitor was fabricated by screwing and sealing the shell of the above-mentioned two-pole nickel coin battery -48-201209116. The electrolysis used herein is a propylene carbonate solution containing triethylmethylammonium tetrafluoroborate at a concentration of 1 mol/L. The self-discharge rate and cycle characteristics of the obtained electric double layer capacitors in a high temperature environment are shown in Table 4 below. -49-201209116 Comparative Example 21 | Bu 04 00 00 Comparative Example 20 CO CO CO C0 (Ο Comparative Example 19 in r - Example 20 g CSJ 00 Example 19 s 〇 | Binder Composition Name I Electrode Active Material Layer Peeling strength (mN/2cm) I self-discharge rate in the temperature environment (%) Cyclic characteristics (%) S3! inch 嗽) (S> 50-201209116 From the results of Table 4, the electrode adhesive of the present invention is used. In the composition (si) and (s7), an electric double layer capacitor which is excellent in both the discharge rate characteristics in a low temperature environment and the electrochemical stability in a high temperature environment can be obtained.