201136009 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種使用鋰合金系負極活性物質之高容量 型鋰離子二次電池用負極及使用它之鋰離子二次電池。 【先前技術】 近年來，由於攜帶式電子機器之急速發展，鋰離子二次電 池等之二次電池的需求逐漸增加，隨著攜帶式電子機器之小 型、重量輕、高機能化，期望高能量密度之電池。 鋰離子二次電池之正極係使用例如作爲正極活性物質之 鋰鈷錯合氧化物等之鋰錯合金屬氧化物，使其與黏著劑樹脂分 散於N-甲基-2-吡咯酮（NMP)中而作成漿體之物塗布於集電 體金屬箔之單面，使溶劑乾燥後，利用輥壓機而進行壓縮成形 所製得。另外，鋰離子二次電池之負極係例如將可吸附釋出鋰 之碳系材料作爲負極活性物質而使用，使其與黏著樹脂分散於 NMP中而作成漿體之物塗布於集電體金屬箔之單面，與正極之 情形同樣地使溶劑乾燥後，利用輥壓機而進行壓縮成形所製 得。以下，將正極之集電體以外之部分稱爲「正極活性物質 層」、將負極之集電體以外之部分稱爲「負極活性物質層」， 此等正極活性物質層、負極活性物質層總稱爲「活性物質層」。 習知該黏著樹脂大多主要使用聚氟化偏乙烯（PVDF )。 然而，將聚氣化偏乙稀作爲黏者樹脂而使用之情形下，集電體 與活性物質層之間的緊貼性及活性物質層中所含之正極活性 物質或負極活性物質、黏著樹脂、導電劑等（總稱爲「組合劑」） 之相互間的緊貼性差’於進行所製作的正極、負極之裁斷、捲 201136009 繞的步驟等之製造步驟時’組合劑之一部分將從集電體剝離/ 脫落而成爲微少短路、電池容量偏異之原因。另外，藉由重複 所獲得之鋰離子二次電池之充放電’尤其由於在負極中之碳系 材料將膨脹/收縮’組合劑將從集電體剝離/脫落，由於組合劑 相互間之緊貼性之降低’將有集電效率降低、發生與鋰之反應 不均而使電池容量逐漸降低之問題。 取代PVDF之黏著樹脂，例如在日本專利特開2〇〇1_68115 號公報（專利文獻1 )中，已介紹矽氧烷改性聚醯胺醯亞胺樹 脂。在專利文獻1中’已介紹藉由將矽氧烷改性聚醯胺醯亞胺 樹脂作爲黏著樹脂而使用’對於將碳系材料作爲負極活性物質 而使用的負極活性物質層之集電體的緊貼性將提高來使充放 電容量提高。 另外’近年來將碳系材料及石墨系材料用於負極之鋰離子 二次電池已實用化。然而，石墨之情形，理論容量之372mAh 遠較鋰金屬之4000 mAh爲差。因此，有人進行具有接近鋰金 屬之理論容量的鋰合金作爲活性物質之負極材料的探討。作爲 負極活性物質所使用的鋰合金可舉例：鋰-錫合金、鋰-鋅合 金、鋰-鉍合金、鋰-鋁合金、鋰-砷合金、鋰-矽合金、鋰-銻合 金等。 但是，與將碳系材料使用於負極活性物質而使用之情形作 一比較，將此等之鋰合金作爲負極活性物質而使用之情形下， 由於使因重複之充放電所造成的膨脹收縮將更進一步變大，負 極材料之機械性損傷之問題將變得顯著，將有初期之充放電效 率、循環特性變差之問題。 201136009 上述之專利文獻1所介紹的矽氧烷改性聚醯胺醯亞胺樹脂 係胺型，使其與酸酐反應而形成醯亞胺鍵結。因此，將鍵合金 作爲負極活性物質而使用之情形下，與將碳系材料作爲負極活 性物質而使用之情形不同，與負極活性物質之緊貼性不佳，將 有未改善循環特性之問題。 先前技術文獻 專利文獻1 :日本專利特開200 1 -68 1 1 5號公報 【發明內容】 〔發明所欲解決之問題〕 本發明係有鑑於如此習用技術之現狀所提出，其目的在於 提供一種鋰離子二次電池用負極及使用它之鋰離子二次電 池’其能夠抑制因伴隨充放電之體積膨脹收縮所造成的電極材 料之機械性損傷’爲高容量且提高初期充放電效率及循環特 性。 〔解決問題之手段〕 本發明人等爲了達成如此之目的而鑽硏的結果，發現：藉 由使用含有能夠形成鋰與合金之金屬的負極活性物質，且將對 銅箔之緊貼力爲1 〇 g/mm以上，且對矽晶圓之緊貼力爲1 0 g/mm以上的聚醯胺醯亞胺樹脂作爲黏著樹脂而使用，由於將 該負極活性物質與黏著樹脂具有優異的緊貼性，以及含有該負 極活性物質及黏著樹脂之負極活性物質層與集電體具有優異 @緊貼性，能夠抑制因伴隨充放電之體積膨脹收縮所造成的電 極材料之機械性損傷，具有優異的初期充放電效率及循環特 性。亦即，本發明係如下所示：[Technical Field] The present invention relates to a negative electrode for a high-capacity lithium ion secondary battery using a lithium alloy-based negative electrode active material, and a lithium ion secondary battery using the same. [Prior Art] In recent years, the demand for secondary batteries such as lithium ion secondary batteries has been increasing due to the rapid development of portable electronic devices. With the small size, light weight, and high performance of portable electronic devices, high energy is expected. Density battery. In the positive electrode of the lithium ion secondary battery, for example, a lithium-substituted metal oxide such as a lithium cobalt-substituted oxide as a positive electrode active material is used, and the adhesive resin is dispersed in N-methyl-2-pyrrolidone (NMP). The slurry formed in the middle is applied to one surface of the current collector metal foil, and the solvent is dried, and then compression-molded by a roll press. In the negative electrode of the lithium ion secondary battery, for example, a carbon-based material capable of adsorbing and releasing lithium is used as a negative electrode active material, and a paste-formed resin is dispersed in NMP to be applied to a current collector metal foil. One side of the film was dried in the same manner as in the case of the positive electrode, and then compression-molded by a roll press. In the following, a portion other than the current collector of the positive electrode is referred to as a "positive electrode active material layer", and a portion other than the current collector of the negative electrode is referred to as a "negative electrode active material layer". These positive electrode active material layers and negative electrode active material layers are collectively referred to as It is an "active material layer". It is known that most of the adhesive resin mainly uses polyfluorinated vinylidene (PVDF). However, in the case where polycondensed ethylene is used as the binder resin, the adhesion between the current collector and the active material layer and the positive electrode active material or the negative electrode active material or the adhesive resin contained in the active material layer are used. When a conductive agent or the like (collectively referred to as "combination agent") has poor adhesion to each other, in the manufacturing steps such as the step of cutting the produced positive electrode and negative electrode, and winding the step 201136009, one part of the composition will be collected. The body peels off/drops and causes a slight short circuit and a difference in battery capacity. In addition, by repeating the charge and discharge of the obtained lithium ion secondary battery 'especially because the carbon-based material in the negative electrode expands/contracts the composition agent from the current collector, the composition is closely adhered to each other. The decrease in the property rate will reduce the collection efficiency and cause a problem that the battery capacity is gradually reduced due to uneven reaction with lithium. In the case of the adhesive resin of the PVDF, the oxime-modified polyamidoximine resin has been described in Japanese Patent Laid-Open Publication No. Hei. No. Hei. In Patent Document 1, 'the current collector of the negative electrode active material layer used for the carbon-based material as the negative electrode active material is used as the adhesive resin by using the siloxane-modified polyamidoximine resin. The adhesion will be improved to increase the charge and discharge capacity. Further, in recent years, lithium ion secondary batteries using a carbon-based material and a graphite-based material for a negative electrode have been put into practical use. However, in the case of graphite, the theoretical capacity of 372 mAh is much worse than the 4000 mAh of lithium metal. Therefore, a discussion has been made on a lithium alloy having a theoretical capacity close to that of lithium metal as a negative electrode material of an active material. The lithium alloy used as the negative electrode active material may, for example, be a lithium-tin alloy, a lithium-zinc alloy, a lithium-niobium alloy, a lithium-aluminum alloy, a lithium-arsenic alloy, a lithium-niobium alloy, a lithium-ruthenium alloy or the like. However, in comparison with the case where a carbon-based material is used for a negative electrode active material, when such a lithium alloy is used as a negative electrode active material, expansion and contraction due to repeated charge and discharge will be more preferable. Further, the problem of mechanical damage of the negative electrode material becomes remarkable, and there is a problem that the initial charge and discharge efficiency and the cycle characteristics are deteriorated. 201136009 The oxime-modified polyamidoximine resin described in Patent Document 1 described above is an amine type which reacts with an acid anhydride to form a quinone bond. Therefore, when the key alloy is used as the negative electrode active material, unlike the case where the carbon-based material is used as the negative electrode active material, the adhesion to the negative electrode active material is not good, and there is a problem that the cycle characteristics are not improved. PRIOR ART DOCUMENT PATENT DOCUMENT 1: Japanese Patent Laid-Open Publication No. JP-A No. Hei. No. Hei. No. Hei. No. Hei. A negative electrode for a lithium ion secondary battery and a lithium ion secondary battery using the same, which are capable of suppressing mechanical damage of an electrode material due to volume expansion and contraction accompanying charge and discharge, and which have high capacity and improved initial charge and discharge efficiency and cycle characteristics . [Means for Solving the Problem] As a result of the inventors of the present invention in order to achieve such a purpose, it has been found that by using an anode active material containing a metal capable of forming lithium and an alloy, the adhesion force to the copper foil is 1醯g/mm or more, and the polyimide amide amide resin having a contact force of 10 g/mm or more on the ruthenium wafer is used as an adhesive resin, and the negative electrode active material and the adhesive resin have excellent adhesion. And the negative electrode active material layer containing the negative electrode active material and the adhesive resin have excellent adhesion to the current collector, and can suppress mechanical damage of the electrode material due to volume expansion and contraction accompanying charge and discharge, and is excellent. Initial charge and discharge efficiency and cycle characteristics. That is, the present invention is as follows:
S 201136009 本發明之鋰離子二次電池用.負極，其特徵係具備在集電體 上所形成的負極活性物質層之負極；該負極活性物質層係包含 含有能夠形成鋰與合金之金屬的負極活性物質與黏著樹脂，該 黏著樹脂係含有對銅箔之緊貼力爲10 g/mm以上，且對矽晶圓 之緊貼力爲1 〇 g/mm以上的聚醯胺醯亞胺樹脂。 於本發明之鋰離子二次電池用負極中，該聚醯胺醯亞胺樹 脂較佳爲其酸成分之一部分置換成由在末端具有羧基、羥基或 胺基之矽氧烷化合物、在末端具有羧基或羥基之丁二烯化合物 及聚烷二醇所構成之族群中所選出的任一種以上之化合物。 本發明之鋰離子二次電池用負極也能夠形成該鋰與合金 之金屬較佳爲由錫、鋁、鉍、砷、矽、鉛、鋅與銻所構成之族 群中所選出的任一種以上之金屬，能夠形成該鋰與合金之金屬 特佳爲含有砂。 本發明也提供一種鋰離子二次電池，其係具備：上述任一 項之鋰離子二次電池用負極、具備在集電體上所形成的正極活 性物質層之正極、在該負極與正極之間由多孔質膜所構成之分 隔膜、與含有電解質之電解液。 [發明之效果] 本發明之鋰離子二次電池用負極係含有能夠形成鋰與合 金之金屬的負極活性物質，也具有與黏著樹脂之緊貼性’以及 負極活性物質層與集電體之間的緊貼性’其結果’能夠容易地 獲得一種鋰離子二次電池用負極及使用它之鋰離子二次電 池’其能夠因伴隨充放電之體積膨脹收縮所造成的電極材料之 機械性損傷，爲高容量且提高初期充放電效率及循環特性。 201136009 【實施方式】 本發明係提供一種鋰離子二次電池用負極及使用它之鋰 離子二次電池，其係藉由將對銅箔及矽晶圓之緊貼性優異的聚 醯胺醯亞胺樹脂作爲負極用黏著樹脂而使用，具有優異的初期 充放電效率及循環耐久性之含有能夠形成鋰與合金之金屬的 負極活性物質。 本發明所用之聚醯胺醯亞胺樹脂係芳香族或脂肪族、脂環 族之聚醯胺醯亞胺，除了緊貼性之外，從強度、彈性模數、耐 電解液性、溶劑溶解性、加工性、成本等之觀點，此等之中， 較佳爲芳香族聚醯胺醯亞胺樹脂。本發明所用之聚醯胺醯亞胺 樹脂能夠利用通常之溶液聚合法而製造，也能夠利用二胺法或 異氰酸酯法等習知方法而製造。 本發明所用之聚醯胺醯亞胺樹脂之製造所用之酸成分，除 了偏苯三酸及其酸‘酐、酸氯化物之外，可舉例：均苯四酸、聯 苯四酸、聯苯磺醯四酸、二苯甲酮四酸、聯苯醚四酸、乙二醇 雙偏苯三酸酐、丙二醇雙偏苯三酸酐等之四酸及此等之酸酐； 草酸、己二酸、丙二酸、癸二酸、壬二酸、十二烷二酸、二羧 基聚丁二烯、二羧基聚（丙烯腈-丁二烯）、二羧基聚（苯乙 烯-丁二烯）等之脂肪族二羧酸；1，4 -環己烷二羧酸、1,3 -環己 烷二羧酸、4,4’-二環己基甲烷二羧酸、二聚物酸等之脂環族二 羧酸；對苯二酸、間苯二酸、二苯基磺醯二酸、二苯基醚二酸、 荼二酸等之芳香族二羧酸；從反應性、耐熱性等之觀點，於此 等酸成分之中’最好爲偏苯三酸酐；從強度 '彈性模數、耐電 解液性之觀點，較佳爲其一部分被取代成均苯四酸酐、二苯甲 201136009 酮四酸酐、聯苯四酸酐者。 本發明之特徵係提供一種鋰離子二次電池’其係藉由將對 銅箔及矽晶圓之具有優異緊貼力之聚醯胺醯亞胺樹脂作爲負 極用之黏著樹脂而使用，具有優異的初期充放電特性及循環耐 久性。因此，較佳爲將該酸成分之一部分置換成末端具有羧 基、羥基或胺基之矽氧烷化合物、末端具有羧基或羥基之丁二 烯化合物、聚伸烷二醇之一種或二種以上。 聚醯胺醯亞胺樹脂之製造所用之二胺（二異氰酸酯）可舉 例：乙二胺、丙二胺、六亞甲二胺等之脂肪族二胺及此等所對 應的二異氰酸酯之六亞甲二異氰酸酯；1,4-環己二胺、l，3-環 己二胺、異佛酮二胺、4,4’-二環己基甲烷二胺等之脂環族二 胺：及此等所對應的二異氰酸酯之異佛酮二異氰酸酯、4,4’-二環己基甲烷二異氰酸酯、間伸苯基二胺、對伸苯基二胺、4,4’-二胺基二苯基甲烷、4,4’-二胺基二苯基醚、4,4’-二胺基二苯基 颯、聯苯胺、聯鄰甲苯胺、2,4-甲苯二胺、2,6-甲苯二胺、二 甲苯二胺、萘二胺等之芳香族二胺以及此等所對應的二異氰酸 酯之間伸苯基二異氰酸酯、對伸苯基二異氰酸酯、二苯基甲烷 -4,4’-二異氰酸酯、二苯基醚-4,4’_二異氰酸酯 '二苯基_4,4’_ 二異氰酸酯、聯鄰甲苯胺二異氰酸酯、2，4_甲苯二異氰酸酯、 2,6 -甲苯二異氰酸酯、二甲苯二異氰酸酯、萘二異氰酸酯；從 耐熱性、溶解性等之觀點，此等之中，較佳爲4，4，-二胺基二 苯基甲烷（二苯基甲烷-4,4，-二異氰酸酯）、2,4-甲苯二胺（2,4-甲苯二異氰酸酯）、聯鄰甲苯胺（聯鄰甲苯胺二異氰酸酯）、 萘二胺（萘二異氰酸酯）、異佛酮二胺（異佛酮二異氰酸酯） 201136009 等。尤其從強度、彈性模數之觀點，較佳爲聯鄰甲苯胺（聯鄰 甲苯胺二異氰酸酯）與萘二胺（萘二異氰酸酯）。 於本發明所用之聚醯胺醯亞胺樹脂中，以改良負極活性物 質、所述之導電劑等之分散性之目的下，能夠共聚合具有離子 性基之化合物。具有與聚醯胺醯亞胺樹脂進行共聚合之離子性 基的化合物，可舉例：酸酐、二羧酸、二異氰酸酯，此等化合 物係含有酚性羥基、磺酸基、膦酸基作爲離子性基，離子性基 也可以形成金屬鹽、四級銨鹽。具體而言，偏苯三酸單鈉鹽、 均苯三酸單鉀鹽、偏苯三酸酐5_羧酸鈉、間苯二酸-5-磺酸鈉、 2-羧乙基磺酸單鉀鹽、羥基間苯二酸-5-磺酸鈉、5-二烷胺基間 苯二酸、5-羥磺基間苯二酸等。從反應性、價格等之觀點，此 等化合物之中較佳爲羥基間苯二酸-5-磺酸鈉、5_羥磺基間苯二 酸，此等化合物可以爲鈉鹽或鉀鹽，另外，也可以爲乙二醇、 丙二醇、新戊二醇、1,4-丁二醇等之二酯化合物。此等之共聚 合量較佳爲0.1至20莫耳％，更佳爲〇.5至10莫耳％，進~ 步較佳爲1至7莫耳％ ’ 〇 · 1莫耳％以下之情形，具有分散性 之改良效果爲小的情形。另外，即使超過2 0莫耳％，分散性 之效果也不改變。 進行聚酿胺酸亞胺樹脂的溶液聚合之情形，藉由在N，N，-二甲基乙醯胺或N -甲基-2-吡咯酮、N，N’-二甲基甲醯胺、厂丁 內·酯等之極性溶劑中，一邊加熱至60至200 °C，一邊進行攪拌 而能夠容易製造。此情形下，必要時能夠將三乙胺、二伸乙基 二胺、一氮雜一環嫌等之有機胺化合物；氟化鉀、氟化鈉、 氟化鉋、甲醇鈉等之金屬化合物用於觸媒。S 201136009 A negative electrode for a lithium ion secondary battery according to the present invention, characterized in that it comprises a negative electrode of a negative electrode active material layer formed on a current collector, and the negative electrode active material layer contains a negative electrode containing a metal capable of forming lithium and an alloy. The active material and the adhesive resin contain a polyamidoquinone imide resin having a bonding force to the copper foil of 10 g/mm or more and a adhesion force to the silicon wafer of 1 〇g/mm or more. In the negative electrode for a lithium ion secondary battery of the present invention, the polyamidoximine resin is preferably partially substituted with one of the acid components to have a siloxane compound having a carboxyl group, a hydroxyl group or an amine group at the terminal, and has a terminal compound at the terminal. Any one or more selected from the group consisting of a butadiene compound of a carboxyl group or a hydroxyl group and a polyalkylene glycol. The negative electrode for a lithium ion secondary battery of the present invention can also form any one of the group selected from the group consisting of tin, aluminum, antimony, arsenic, antimony, lead, zinc, and antimony. The metal, which is capable of forming the metal of the lithium and the alloy, is particularly preferably sand-containing. The present invention also provides a lithium ion secondary battery comprising: the negative electrode for a lithium ion secondary battery according to any one of the above, a positive electrode including a positive electrode active material layer formed on the current collector, and the negative electrode and the positive electrode A separator film composed of a porous membrane and an electrolyte containing an electrolyte. [Effects of the Invention] The negative electrode for a lithium ion secondary battery of the present invention contains a negative electrode active material capable of forming a metal of lithium and an alloy, and also has adhesion to the adhesive resin and between the negative electrode active material layer and the current collector. The adhesion 'the result' can easily obtain a negative electrode for a lithium ion secondary battery and a lithium ion secondary battery using the same, which can cause mechanical damage of the electrode material due to volume expansion and contraction accompanying charge and discharge. It is high in capacity and improves initial charge and discharge efficiency and cycle characteristics. [Embodiment] The present invention provides a negative electrode for a lithium ion secondary battery and a lithium ion secondary battery using the same, which is excellent in adhesion to a copper foil and a tantalum wafer. The amine resin is used as an adhesive resin for a negative electrode, and contains a negative electrode active material capable of forming a metal of lithium and an alloy, which has excellent initial charge and discharge efficiency and cycle durability. The polyamidoximine resin used in the present invention is an aromatic or aliphatic or alicyclic polyamidoximine which has strength, modulus of elasticity, electrolyte resistance, and solvent dissolution in addition to adhesion. Among the viewpoints of properties, workability, cost, and the like, among these, an aromatic polyamidoximine resin is preferred. The polyamidoximine resin used in the present invention can be produced by a usual solution polymerization method, or can be produced by a conventional method such as a diamine method or an isocyanate method. The acid component used in the manufacture of the polyamidoximine resin used in the present invention may be, for example, pyromellitic acid, biphenyltetracarboxylic acid or biphenyl, in addition to trimellitic acid and its acid anhydride and acid chloride. Sulfuric acid, benzophenone tetracarboxylic acid, diphenyl ether tetracarboxylic acid, ethylene glycol trimellitic anhydride, propylene glycol trimellitic anhydride, and the like; and acid anhydride; oxalic acid, adipic acid, malonic acid, azelaic acid An aliphatic dicarboxylic acid such as azelaic acid, dodecanedioic acid, dicarboxypolybutadiene, dicarboxy poly(acrylonitrile-butadiene), dicarboxy poly(styrene-butadiene); , an alicyclic dicarboxylic acid such as 4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 4,4'-dicyclohexylmethanedicarboxylic acid, dimer acid or the like; An aromatic dicarboxylic acid such as an acid, an isophthalic acid, a diphenylsulfonic acid, a diphenyl ether diacid or a sebacic acid; and among such an acid component, from the viewpoints of reactivity, heat resistance, and the like 'preferably trimellitic anhydride; from the viewpoint of strength 'elastic modulus, electrolyte resistance, it is preferred that a part thereof is substituted with pyromellitic anhydride, diphenyl 201138009 ketone four Dianhydride, biphenyl tetracarboxylic acid anhydride were. A feature of the present invention is to provide a lithium ion secondary battery which is excellent in use as an adhesive resin for a negative electrode by using a polyimide resin having excellent adhesion to copper foil and tantalum wafer. Initial charge and discharge characteristics and cycle durability. Therefore, it is preferred to partially replace one of the acid components with one or two or more kinds of a decane compound having a carboxyl group, a hydroxyl group or an amine group at the terminal, a butadiene compound having a carboxyl group or a hydroxyl group at the terminal, and a polyalkylene glycol. The diamine (diisocyanate) used in the production of the polyamidoximine resin can be exemplified by an aliphatic diamine such as ethylenediamine, propylenediamine or hexamethylenediamine, and the corresponding diisocyanate of the hexamethylenediamine. Methyl diisocyanate; alicyclic diamines such as 1,4-cyclohexanediamine, 1,3-cyclohexanediamine, isophorone diamine, 4,4'-dicyclohexylmethanediamine: and the like Corresponding diisocyanate isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, meta-phenylene diamine, p-phenylenediamine, 4,4'-diaminodiphenylmethane , 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl hydrazine, benzidine, o-toluidine, 2,4-toluenediamine, 2,6-toluenediamine Between the aromatic diamines such as xylene diamine and naphthalenediamine, and the corresponding diisocyanates, phenyl diisocyanate, p-phenylene diisocyanate, diphenylmethane-4,4'-diisocyanate , diphenyl ether-4,4'-diisocyanate 'diphenyl-4,4'-diisocyanate, ortho-toluidine diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, Xylene diisocyanate or naphthalene diisocyanate; from the viewpoints of heat resistance, solubility, etc., among these, 4,4,-diaminodiphenylmethane (diphenylmethane-4,4,- is preferable). Diisocyanate), 2,4-toluenediamine (2,4-toluene diisocyanate), o-toluidine (toluidine diisocyanate), naphthalenediamine (naphthalene diisocyanate), isophorone diamine (different Fosone diisocyanate) 201136009 and so on. Particularly, from the viewpoint of strength and modulus of elasticity, it is preferably o-toluidine (ortho-toluidine diisocyanate) and naphthalenediamine (naphthalene diisocyanate). In the polyamidoximine resin used in the present invention, a compound having an ionic group can be copolymerized for the purpose of improving the dispersibility of the negative electrode active material and the above-mentioned conductive agent. Examples of the compound having an ionic group copolymerized with a polyamidoximine resin include an acid anhydride, a dicarboxylic acid, and a diisocyanate, and these compounds contain a phenolic hydroxyl group, a sulfonic acid group, and a phosphonic acid group as an ionic property. The ionic group may also form a metal salt or a quaternary ammonium salt. Specifically, trimellitic acid monosodium salt, trimesic acid monopotassium salt, trimellitic anhydride 5-carboxylate sodium, isophthalic acid-5-sulfonic acid sodium, 2-carboxyethylsulfonic acid monopotassium salt, hydroxyl group Sodium isophthalate-5-sulfonate, 5-dialkylaminoisophthalic acid, 5-hydroxysulfoisophthalic acid, and the like. From the viewpoints of reactivity, price, etc., among these compounds, sodium hydroxy isophthalate-5-sulfonate and 5-hydroxysulfoisophthalic acid are preferred, and these compounds may be sodium or potassium salts. Further, it may be a diester compound such as ethylene glycol, propylene glycol, neopentyl glycol or 1,4-butanediol. The amount of such copolymerization is preferably from 0.1 to 20 mol%, more preferably from 55 to 10 mol%, and further preferably from 1 to 7 mol% '〇·1 mol% or less The improvement effect with dispersibility is small. Further, even if it exceeds 20% by mole, the effect of dispersibility does not change. In the case of solution polymerization of a polyamidoimine resin, by N,N,-dimethylacetamide or N-methyl-2-pyrrolidone, N,N'-dimethylformamide In a polar solvent such as a butyl ester or an ester, it can be easily produced by stirring while heating to 60 to 200 °C. In this case, if necessary, an organic amine compound such as triethylamine, diethylidene diamine or monoazapine may be used; a metal compound such as potassium fluoride, sodium fluoride, fluorinated planer or sodium methoxide may be used. catalyst.
S -10- 201136009 於本發明所用之聚醯胺醯亞胺樹脂具有對集電體及負極 活性物質之緊貼性而承受充放電時之負極活性物質之膨脹'收 縮的必要，因此，對於作爲集電體通常所用之銅箔以及作爲替 代負極活性物質之矽晶圓的緊貼力任一種皆必須爲1 0 g/mm以 上（較佳爲20 g/mm以上）。對於聚醯胺醯亞胺樹脂之銅箔及 矽晶圓的緊貼力之上限並未予以特別限制，若爲1 00 g/mm左 右則爲足夠。與矽晶圓具有優異的緊貼性之聚醯胺醯亞胺樹脂 係與負極活性物質具有優異的緊貼性，藉由使用該樹脂而提供 具有優異的初期及重複充放電之鋰離子二次電池。 若聚醯胺酶亞胺樹脂對銅箱之緊貼力低於10 g/mm時，無 法承受初期及重複充放電時之膨脹、收縮而從集電體剝離，鋰 離子之移動將受到妨礙且容量將降低。另外，若聚醯胺醯亞胺 樹脂對銅箔之緊貼力低於1 〇 g/mm時，於初期及重複充放電 時，負極活性物質層將受到破壞，鋰離子之移動將受到妨礙且 充放電容量將降低。 另外，從聚醯胺醯亞胺樹脂對銅箔及矽晶圓之緊貼性之觀 點，本發明所用之聚醯胺醯亞胺樹脂係其酸成分之一部分置換 成由在末端具有羧基、羥基或胺基之矽氧烷化合物、在末端具 有羧基或羥基之丁二烯化合物及聚烷二醇之一種或二種以上 之化合物。藉由此等之化合物與異氰酸酯化合物進行反應，能 夠將醯胺鍵、脲鍵、胺甲酸酯鍵等導入聚醯胺醯亞胺樹脂骨架 中，與銅箔 '矽晶圓之緊貼性將提高。尤其，酸成分之一部分 較佳爲置換成在末端具有羧基、羥基、胺基之矽氧烷化合物的 聚醯胺醯亞胺樹脂。可舉例：在末端含有羧基、羥基、胺基、S -10- 201136009 The polyamidoximine resin used in the present invention has a function of adhering to a current collector and a negative electrode active material, and is required to undergo expansion and contraction of the negative electrode active material during charge and discharge, and therefore, The contact force of the copper foil generally used for the current collector and the tantalum wafer as a substitute for the negative electrode active material must be 10 g/mm or more (preferably 20 g/mm or more). The upper limit of the adhesion between the copper foil and the tantalum wafer of the polyimide film is not particularly limited, and it is sufficient if it is about 100 g/mm. The polyamidoximine resin having excellent adhesion to the ruthenium wafer has excellent adhesion to the negative electrode active material, and provides lithium ion secondary having excellent initial and repeated charge and discharge by using the resin. battery. If the adhesion force of the polyamidase imine resin to the copper box is less than 10 g/mm, it cannot withstand the expansion and contraction at the initial stage and repeated charge and discharge, and is peeled off from the current collector, and the movement of lithium ions is hindered and The capacity will decrease. In addition, when the adhesion strength of the polyamide amide resin to the copper foil is less than 1 〇g/mm, the negative electrode active material layer is destroyed at the initial stage and repeated charge and discharge, and the movement of lithium ions is hindered. The charge and discharge capacity will decrease. Further, from the viewpoint of the adhesion of the polyimide film to the copper foil and the tantalum wafer, the polyamidoximine resin used in the present invention is partially substituted with one of the acid components to have a carboxyl group and a hydroxyl group at the terminal. Or an amino group-containing oxane compound, a butadiene compound having a carboxyl group or a hydroxyl group at the terminal, and one or more compounds of a polyalkylene glycol. By reacting such a compound with an isocyanate compound, a guanamine bond, a urea bond, a urethane bond or the like can be introduced into the polyamido ruthenium resin skeleton, and the adhesion to the copper foil 矽 wafer will be improve. In particular, a part of the acid component is preferably a polyamidoximine resin which is substituted with a siloxane compound having a carboxyl group, a hydroxyl group or an amine group at the terminal. For example, it has a carboxyl group, a hydroxyl group, an amine group at the end,
S 201136009 縮水甘油醚基之矽氧烷化合物係重量平均分子量爲1 00 0至 10000之二甲基聚矽氧烷或甲基苯基聚矽氧烷。具體而言，可 舉例：X-22-1660B3C信越化學工業（股）製）、KF6003 C信 越化學工業（股）製）等。另外，對於聚醯胺醯亞胺樹脂而言， 使用在末端含有縮水甘油醚基之矽氧烷化合物而進行末端改 性，從與銅箔、矽晶圓的緊貼性之觀點也較佳。 另外，在末端含有羧基、羥基之丁二烯化合物，可舉例： 重量平均分子量爲1 000至1 0000之聚丁二烯、丙烯腈丁二烯、 苯乙烯丁二烯等，具體而言，可舉例：Hypro CTBN系列（PTI (股）製）等。藉由此等之化合物與異氰酸酯進行反應，能夠 將醯胺鍵、胺甲酸酯鍵導入聚醯胺醯亞胺樹脂骨架中，與銅 箔、矽晶圓之緊貼性將被提高。 聚烷二醇可舉例：重量平均分子量爲400至10000之聚乙 二醇、聚丙二醇、聚四乙二醇等。藉由此等之化合物與異氰酸 酯化合物進行反應，能夠將胺甲酸酯鍵導入聚醯胺醯亞胺樹脂 骨架中，將提高與銅箔、矽晶圓之緊貼性。 該矽氧烷化合物、丁二烯化合物、聚烷二醇化合物之共聚 合量係於聚醯胺醯亞胺樹脂中，較佳爲0.1至70重量％，更 佳爲0.5至50重量％，進一步較佳爲1至30重量％。若該共 聚合量低於0.1重量％的話，具有上述之緊貼性的改良效果爲 不足之情形；若超過70重量％時，對電解液之膨潤將變大’ 具有初期及重複充放電容量將降低之傾向。 本發明所用之聚醯胺醯亞胺樹脂之分子量係以對數黏度 較佳爲0.5 dl/g以上，雖然上限並無特別限制，從溶液之操作S 201136009 The glycidyl ether-based oxane compound is a dimethylpolysiloxane or a methylphenyl polyoxyalkylene having a weight average molecular weight of from 100 to 10,000. Specifically, it can be exemplified by X-22-1660B3C Shin-Etsu Chemical Co., Ltd., KF6003 C-Vietnam Chemical Industry Co., Ltd., and the like. Further, the polyamidoximine resin is preferably modified from the viewpoint of adhesion to a copper foil or a tantalum wafer by using a fluorinated ether compound having a glycidyl ether group at the terminal end. Further, the butadiene compound having a carboxyl group or a hydroxyl group at the terminal may, for example, be a polybutadiene having a weight average molecular weight of 1,000 to 100, acrylonitrile butadiene, styrene butadiene, or the like, specifically, For example: Hypro CTBN series (PTI (share) system) and so on. By reacting such a compound with an isocyanate, a guanamine bond or a urethane bond can be introduced into a polyamidoximine resin skeleton, and adhesion to a copper foil or a tantalum wafer can be improved. The polyalkylene glycol can be exemplified by polyethylene glycol, polypropylene glycol, polytetraethylene glycol or the like having a weight average molecular weight of 400 to 10,000. By reacting such a compound with an isocyanate compound, the urethane bond can be introduced into the polyamidoximine resin skeleton, and the adhesion to the copper foil or the tantalum wafer can be improved. The copolymerization amount of the decane compound, the butadiene compound, and the polyalkylene glycol compound is in the polyamidoximine resin, preferably from 0.1 to 70% by weight, more preferably from 0.5 to 50% by weight, further It is preferably from 1 to 30% by weight. When the amount of the copolymerization is less than 0.1% by weight, the improvement effect of the above-mentioned adhesion is insufficient, and if it exceeds 70% by weight, the swelling of the electrolyte becomes large, and the initial and repeated charge and discharge capacities are Reduce the tendency. The molecular weight of the polyamidoximine resin used in the present invention is preferably 0.5 dl/g or more in logarithmic viscosity, although the upper limit is not particularly limited, from the operation of the solution.
S -12- 201136009 更容易性、漿體之製作容易性等之觀點’較佳爲2.5 dl/g ^ 若該對數黏度低於0.5 dl/g時，具有聚醯胺醯亞胺樹脂之 性將變低之傾向，於使用該樹脂之鋰離子二次電池中，具 據因充放電所造成的體積膨脹、收縮而無法抑制電極材料 械性損傷之情形。爲了增大該對數黏度，聚合溫度、時間 製造條件的控制也爲有效，縮小酸成分/二胺（二異氰酸 成分之莫耳比特別有效。 本發明所用之負極活性物質，只要與鋰能夠形成合金 屬的話，並未予以特別限制，具體而言，能夠使用由錫（S 鋁（A1)、矽（Si )、鉍（Bi )、鋅（Zn )、砷（As )、銻 及鉛（Pb)所構成之族群中所選出的一種以上之金屬。本 中之負極活性物質能夠以金屬粉末之狀態下使用，也可以 屬單體所構成，另外，也可以爲氧化物及此等之合金。此 中，較佳爲Sn、Si及含有此等之氧化物或合金，含有Si特 含有Sn或Si之合金粉末之情形，Sn或Si之至少一種的 比例較佳作成30至95重量％，更佳作成40至85重量％ 有Sn或Si之合金，例如，可舉例：錫-鐵合金、錫-鎳合 錫-銅合金、錫-辞合金、錫-駄合金、砍-欽合金、砍-錬合金 於本發明中’於製造鋰離子二次電池用負極之際，塗 集電體之組合劑中摻合導電劑。導電劑並未予以特別限制 舉例：Ketjen碳黑或乙炔碳黑、石墨等之碳黑類；陰離子 陽離子系、非離子性及兩性之界面活性劑；聚噻吩、聚乙 聚苯胺等之導電性聚合物等。於此，所謂聚苯胺係指將已 無機酸、十二烷基苯磺酸等之有機質子酸摻雜劑之有機 义下。 強靭 有根 之機 等之 酯） 之金 η )、 (Sb ) 發明 由金 等之 F佳。 含有 。含 金、 ί等。 布於 ，可 :系、 ，炔、 摻雜 溶劑 5 -13- .201136009 中’能夠對氧化聚合的聚苯胺衍生物進行溶解或分散者。於此 等之中’較佳爲導電性之濕度依存性少且對聚醯胺醯亞胺具有 優異的分散性相溶性之碳黑、聚苯胺。 於本發明之集電體中，使用銅、鋁等之金屬箔、篩孔型之 多孔金屬、穿孔金屬等。 本發明之鋰離子二次電池用負極能夠利用習知方法而適 合製造。亦即’在集電體上直接塗布負極活性物質、導電劑、 聚醯胺醯亞胺樹脂之分散液（組合劑）後，進行乾燥，必要時， 能夠利用熱輥或熱板而進行壓縮。此情形下，負極活性物質層 乾燥後之厚度較佳爲30至200 //m，更佳爲50至100 負 極活性物質層之厚度低於3 0 //m之情形下，由於負極活性物質 量少，於使用它之鋰離子二次電池中，將有充放電容量不足之 情形：另外，負極活性物質層之厚度超過2 0 0 //m之情形下， 於捲繞負極之步驟中，具有產生裂痕之憂慮。 於負極活性物質層之形成所用之分散液中，負極活性物 質、導電劑、聚醯胺醯亞胺樹脂之重量比率較佳爲負極活性物 質：導電劑：聚醯胺醯亞胺樹脂=97至80 : 0至5 : 3至20， 更佳爲96至80: 1至5: 3至15。分散液中之負極活性物質之 重量比率超過97之情形下，具有與集電體之緊貼性將降低之 傾向；另外，負極活性物質之重量比率低於8 0之情形下，具 有電池特性將降低之傾向。另外，分散液中之導電劑的重量比 率超過5之情形下，具有電池容量將降低之傾向。再者，分散 液中之聚醯胺醯亞胺樹脂的重量.比率低於3之情形下，具有與 集電體之緊貼性將降低之傾向；另外，聚醯胺醯亞胺樹脂的重 -14- 201136009 量比率超過20之情形下，具有電池特性將降低之傾向》 另外，該分散液係固形物濃度較佳爲30重量％以上，更 佳爲40重量％以上。分散液之固形物濃度低於3 〇重量％之情 形下，由於分散液黏度降低，因而具有塗布適合性將變差之傾 向。另外，從分散液的良好流動性之理由，該分散液之固形物 濃度較佳爲60重量％以下。 該分散液能夠使用分散機、3輥磨機、砂磨機、球磨機、 行星式磨機、磨碎機等之通常分散機而調製。另外，於不損害 本發明效果之範圍內，能夠摻合分散劑、無機塡料、平坦劑、 消泡劑、其他樹脂（例如聚酯、聚醯胺、聚醯亞胺、聚胺甲酸 酯等）、矽氧烷系脫模劑、交聯劑等》交聯劑可舉例：2官能 以上之環氧樹脂、三聚氰胺樹脂、異氰酸酯化合物。 另外’本發明也提供一種針對具備如下構造之鋰離子二次 電池：上述之本發明的鋰離子二次電池用負極、具備在集電體 上所形成的正極活性物質層之正極、在該負極與正極之間由多 孔質膜所構成的分隔膜與含有電解質之電解液。 本發明之鋰離子二次電池之正極所用之正極活性物質係 使用Li Co 〇2 ' Li Μη204等之鋰複合氧化物，除了此等之正極活 性物質之外’正極活性物質層中也包含導電劑、黏著樹脂、 LhC〇3等。黏著樹脂可使用上述之負極所用之聚醯胺醯亞胺樹 月旨、聚偏氟乙烯、偏氟乙烯-六氟丙烯共聚物、苯乙烯-丁二烯 共聚物等。正極中之集電體能夠適合採用作爲負極中之集電體 所上述者。 本發明之鋰離子二次電池所用之分隔膜能夠使用習知所S -12- 201136009 The viewpoint of easiness, ease of preparation of the slurry, etc. 'preferably 2.5 dl / g ^ If the logarithmic viscosity is less than 0.5 dl / g, the properties of the polyamidoximine resin will be In the lithium ion secondary battery using the resin, it is difficult to suppress mechanical damage of the electrode material due to volume expansion and contraction due to charge and discharge. In order to increase the logarithmic viscosity, the control of the polymerization temperature and the time production conditions is also effective, and the reduction of the acid component/diamine (the molar ratio of the diisocyanate component is particularly effective. The negative electrode active material used in the present invention can be used only with lithium. The formation of the metal is not particularly limited, and specifically, tin (S aluminum (A1), bismuth (Si), bismuth (Bi), zinc (Zn), arsenic (As), antimony, and lead can be used. One or more metals selected from the group consisting of Pb). The negative electrode active material in the present invention may be used in the form of a metal powder, or may be a monomer, or may be an oxide or an alloy thereof. Preferably, in the case of Sn, Si, and an oxide or alloy containing the same, and the alloy powder containing Si or Sn is contained, the ratio of at least one of Sn or Si is preferably 30 to 95% by weight. More preferably, 40 to 85% by weight of an alloy having Sn or Si, for example, tin-iron alloy, tin-nickel tin-copper alloy, tin-rhen alloy, tin-bismuth alloy, chop-champ alloy, chopped- Niobium alloy in the invention 'making lithium ion secondary electricity When the negative electrode is used, the conductive agent is blended with the conductive agent. The conductive agent is not particularly limited. Examples are: Ketjen carbon black or acetylene black, graphite and the like carbon black; anionic cation, nonionic and An amphoteric surfactant; a conductive polymer such as polythiophene or polyethene; etc. Here, the term "polyaniline" refers to an organic protonic acid dopant such as an inorganic acid or dodecylbenzenesulfonic acid. Under the organic right. Firming the roots of the machine, etc.) The gold η), (Sb) The invention is better than the gold of F. Contains. Contains gold, ί, etc. The solvent can be dissolved or dispersed in an oxidatively polymerized polyaniline derivative in a system, an alkyne or a doping solvent 5 -13-.201136009. Among these, carbon black and polyaniline which are less in dependence on conductivity and have excellent dispersibility compatibility with polyamidolimine are preferred. In the current collector of the present invention, a metal foil such as copper or aluminum, a mesh type porous metal, a perforated metal or the like is used. The negative electrode for a lithium ion secondary battery of the present invention can be suitably produced by a known method. That is, the negative electrode active material, the conductive agent, and the dispersion of the polyamidoximine resin (combination agent) are directly applied to the current collector, and then dried, and if necessary, compressed by a hot roll or a hot plate. In this case, the thickness of the negative electrode active material layer after drying is preferably from 30 to 200 //m, more preferably from 50 to 100. The thickness of the negative electrode active material layer is less than 30 //m, due to the negative electrode active material quality. In the lithium ion secondary battery using the same, there is a case where the charge and discharge capacity is insufficient. In addition, in the case where the thickness of the negative electrode active material layer exceeds 200 μm, in the step of winding the negative electrode, Worries about cracks. In the dispersion for forming the negative electrode active material layer, the weight ratio of the negative electrode active material, the conductive agent, and the polyamidoximine resin is preferably the negative electrode active material: conductive agent: polyamidoximine resin = 97 to 80 : 0 to 5 : 3 to 20, more preferably 96 to 80: 1 to 5: 3 to 15. When the weight ratio of the negative electrode active material in the dispersion exceeds 97, the adhesion to the current collector tends to be lowered; and when the weight ratio of the negative electrode active material is less than 80, the battery characteristics will be Reduce the tendency. Further, when the weight ratio of the conductive agent in the dispersion exceeds 5, the battery capacity tends to decrease. Further, in the case where the weight ratio of the polyamidoximine resin in the dispersion is less than 3, the adhesion to the current collector tends to be lowered; in addition, the weight of the polyamide amine imide resin is heavy. -14- 201136009 When the amount ratio exceeds 20, the battery characteristics are lowered. Further, the dispersion solid content is preferably 30% by weight or more, and more preferably 40% by weight or more. In the case where the solid content of the dispersion is less than 3% by weight, the viscosity of the dispersion is lowered, so that the coating suitability is deteriorated. Further, the solid content of the dispersion is preferably 60% by weight or less from the viewpoint of good fluidity of the dispersion. The dispersion can be prepared by using a usual disperser such as a disperser, a 3-roll mill, a sand mill, a ball mill, a planetary mill, or an attritor. Further, it is possible to blend a dispersant, an inorganic pigment, a flat agent, an antifoaming agent, and other resins (for example, polyester, polyamide, polyimine, polyurethane) within a range not impairing the effects of the present invention. Examples of the crosslinking agent, such as a cyclopentane-based release agent, a crosslinking agent, etc., may be exemplified by a bifunctional or higher epoxy resin, a melamine resin, or an isocyanate compound. In addition, the present invention also provides a lithium ion secondary battery having the following structure: the negative electrode for a lithium ion secondary battery of the present invention, the positive electrode including the positive electrode active material layer formed on the current collector, and the negative electrode A separator film composed of a porous membrane and an electrolyte containing an electrolyte are provided between the cathode and the cathode. The positive electrode active material used for the positive electrode of the lithium ion secondary battery of the present invention is a lithium composite oxide such as Li Co 〇 2 ' Li Μ η 204, and the positive electrode active material layer contains a conductive agent in addition to the positive electrode active material. , adhesive resin, LhC〇3, etc. As the adhesive resin, a polyamidoquinone imide, a polyvinylidene fluoride, a vinylidene fluoride-hexafluoropropylene copolymer, a styrene-butadiene copolymer or the like which is used for the above negative electrode can be used. The current collector in the positive electrode can be suitably used as the current collector in the negative electrode. The separator film used for the lithium ion secondary battery of the present invention can use a conventional one.
S -15- 201136009 用之分隔膜。具體而言’可舉例：利用聚乙烯、聚丙烯等所形 成的聚烯烴系多孔膜；聚醯亞胺、聚醯胺酿亞胺等所形成的高 耐熱多孔膜；利用該聚烯烴系多孔膜與該高耐熱多孔膜之複合 膜；芳香族聚醯胺、聚醯亞胺、聚醯胺醯亞胺等所形成的不織 布等。 本發明所使用的電解質係由鋰鹽與電解液所構成，可使用 習知之電解質。電解液可舉例：由例如四氫呋喃、苯、甲苯、 三氟甲苯、異丙醇、二甲基碳酸酯、伸乙基亞甲基碳酸酯、二 乙基碳酸酯、甲基丙基碳酸酯、伸丙基碳酸酯、丙基醋酸酯、 甲基醋酸酯、乙基醋酸酯、二甘二甲醚等所選出的一種以上。 另外’鋰鹽可使用由 LiPF6、LiS03CF3、LiN( S02CF3)2、LiC104 等所選出的一種以上。 實施例 以下’顯示實施例而具體地加以說明，本發明係根據此等 之實施例而未予以限制。還有，實施例中之測定値係利用以下 之方法所測出之値。 (1 )對數黏度 將聚醯胺醯亞胺樹脂溶液倒入水中，於30°C，使用烏氏 (Ubbelohde)黏度管而測定將利用水洗淨使其沉澱的固形物 後所乾燥的聚合物0.5 g溶解於100 ml之NMP(N -甲基-2-吡 咯酮）中之溶液而測出。 (2 )對銅箔之緊貼力 利用0.1N稀鹽酸洗淨18ym壓延銅箔的光澤面，使乾燥 後之厚度成爲20 //m左右的方式來塗布聚醯胺醯亞胺樹脂溶 s -16- 201136009 液，進行150°C/3小時、25 0°C/30分鐘之乾燥、熱處理。使此 塗布銅箔1 mm之細線將殘留的方式來利用氯化銅水溶液進行 蝕刻，使用東洋Baldwin公司之Tensilon，於25 °C、65%RH 環境下，拉伸速度200 mm/分鐘測出銅箔與聚醯胺醯亞胺樹脂 之9 0度剝離強度。 (3 )對矽晶圓之緊貼力 將聚醯胺醯亞胺樹脂溶液塗布於矽晶圓之鏡面側，利用與 對銅箔之加工相同條件，進行乾燥、熱處理。將5 mm寬度之 刻痕劃入聚醯胺醯亞胺膜側，使用東洋 Baldwin公司之 Tensilon，於25 °C、65% RH環境下，拉伸速度200 mm/分鐘測 出剝離強度。 (4)充放電效率及循環耐久性 針對在實施例所作成的各電池，以〇 . 2 C進行充放電試驗， 求出首次及重複30次時之充放電效率。 充放電效率=〔（放電容量/充電容量）xl〇〇(%)〕 (聚醯胺醯亞胺樹脂A之合成） 於附有冷凝管與氮氣導入口之4 口燒瓶中，使固形物濃度 成爲20重量％的方式來將1莫耳之二苯基甲烷-4,4’-二異氰酸 酯（MDI) 、0.025莫耳之X-22-1660B3 (信越化學工業（股） 製、二胺丙基苯基甲基聚矽氧烷、重量平均分子量：4400 )、 〇·〇1莫耳之氟化鉀與N-甲基-2-吡咯酮（NMP) —倂進行進料， 於室溫一邊攪拌且一邊使其反應1小時左右後，使固形物濃度 成爲2〇重量％的方式來將0.975莫耳之偏苯三酸酐（TM A ) 一併追加於NMP中，進行120°C/2小時、150°C/5小時之反應。 5 -17- 201136009 其後，使固形物濃度成爲1 5重量％的方式來利用NMP稀釋。 所獲得之聚醯胺醯亞胺樹脂A的含矽氧烷爲24重量％、對數 黏度爲0.72 dl/g。 (聚醯胺醯亞胺樹脂B之合成） 使用與上述之聚醯胺醯亞胺樹脂A合成之情形相同的_ 置，使固形物濃度成爲2〇重量％的方式來將0.95莫耳$ TMA、重量平均分子量爲850的0.05莫耳之聚四亞甲二醇 (PTG) 、0.8莫耳之聯鄰甲苯胺二異氰酸酯、0.2莫耳之2,4_ 亞苄基二異氰酸酯、〇.〇1莫耳之氟化鉀與NMP —併進行進料， —邊攪拌且一邊使其6〇°C/l小時、l2〇°C/5小時左右反應後， 一邊冷卻且一邊使固形物濃度成爲15重量％的方式來利 NMP稀釋。所獲得之聚醯胺醯亞胺樹脂B的PTG含量爲u s 量％、對數黏度爲1.24 dl/g。 (聚醯胺醯亞胺樹脂C之合成） 於附有冷凝管與氮氣導入口之4 口燒瓶中，使固形物濃度 成爲20重量％的方式來將0.975莫耳之TM A、0.025莫耳之末 端羧基丙烯腈-丁二烯（PTIJap an (股）製、CTBN 1300x13、 重量平均分子量：3500) 、1莫耳之MDI、0.01莫耳之氟化鉀 與NMP —倂進行進料，使其120°C/1.5小時、180°C/5小時反 應後，一邊冷卻且一邊使固形物濃度成爲15重量％的方式來 利用 NMP稀釋。所獲得之聚醯胺醯亞胺樹脂C的 CTBN 1300x13之含量爲20重量％、對數黏度爲1_2〇 dl/g。 (聚醯胺醯亞胺樹脂D之合成） 於附有冷凝管與氮氣導入口之4 口燒瓶中’使固形物濃度 -18 * 201136009 成爲20重量％的方式來將0.95莫耳之TMA、KF6003( 學工業（股）製、〇·〇1莫耳之二羥基丙基二甲基聚矽氧 價：22mgKOH/g)、重量平均分子量爲8 50的0.04莫耳3 1莫耳之MDI、0.01莫耳之氟化鉀與NMP —倂進行進 其6〇°C/l小時、l2〇°C/2小時、l5〇°C/5小時反應後，一 且一邊使固形物濃度成爲15重量％的方式來利用NMP 所獲得之聚醯胺醯亞胺樹脂D的矽氧烷含量爲11·8重 PTG之含量爲8.0重量％、對數黏度爲0.98 dl/g。 (聚醯胺醯亞胺樹脂E之合成） 於附有冷凝管與氮氣導入口之4 口燒瓶中，使固形 成爲 20重量％的方式來將 1莫耳之 TMA、0.0015 KF6003、分子量爲850的0.0005莫耳之PTG、1莫耳之 0.01莫耳之氟化鉀與NMP —倂進行進料，進行60°c/l 120°C/2小時、150°C/5小時之反應後，一邊冷卻且一邊 物濃度成爲1 5重量％的方式來利用NMP稀釋。所獲得 胺醯亞胺樹脂E的矽氧烷含量爲0.19重量％、PTG之 0.12重量％、對數黏度爲1.02 dl/g。 (聚醯胺醯亞胺樹脂F之合成） 於附有冷凝管與氮氣導入口之4 口燒瓶中’使固形 成爲20重量％的方式來將0.65莫耳之TMA、0_05 KF 6003、分子量爲850的0.35莫耳之PTG、1莫耳之 〇.〇1莫耳之氟化鉀與NMP —倂進行進料，進行60它〆1 l2〇°C/2小時、i50°C/5小時之反應後，一邊冷卻且—邊 物濃度成爲15重量％的方式來利用NMP稀釋。所獲得 信越化 院、OH :PTG、 料，使 邊冷卻 稀釋。 量％、 物濃度 莫耳之 MDI、 小時、 使固形 之聚醯 含量爲 物濃度 莫耳之 MDI、 小時、 使固形 之聚醯S -15- 201136009 Used as a separator film. Specifically, 'a polyolefin-based porous film formed of polyethylene, polypropylene, or the like; a highly heat-resistant porous film formed of polyimide, polyamine, or the like; and the polyolefin-based porous film A composite film formed with the high heat resistant porous film; a nonwoven fabric formed of an aromatic polyamide, a polyimide, a polyimide, or the like. The electrolyte used in the present invention is composed of a lithium salt and an electrolytic solution, and a conventional electrolyte can be used. The electrolyte can be exemplified by, for example, tetrahydrofuran, benzene, toluene, benzotrifluoride, isopropanol, dimethyl carbonate, ethyl methylene carbonate, diethyl carbonate, methyl propyl carbonate, and One or more selected from the group consisting of propyl carbonate, propyl acetate, methyl acetate, ethyl acetate, and diglyme. Further, as the lithium salt, one or more selected from LiPF6, LiS03CF3, LiN(S02CF3)2, LiC104 and the like can be used. EXAMPLES The following is a detailed description of the embodiments, and the present invention is not limited by the examples. Further, the measurement enthalpy in the examples was measured by the following method. (1) Logarithmic viscosity The polyamidoximine resin solution was poured into water, and the polymer dried after washing the solid matter precipitated with water was measured at 30 ° C using an Ubbelohde viscosity tube. The solution was dissolved in 100 ml of NMP (N-methyl-2-pyrrolidone) to determine the solution. (2) Adhesive force against copper foil The surface of the copper foil of 18 μm is rolled by 0.1 N diluted hydrochloric acid, and the thickness of the dried copper foil is about 20 //m. 16- 201136009 Liquid, dried and heat treated at 150 ° C / 3 hours, 25 0 ° C / 30 minutes. The thin wire of 1 mm of the coated copper foil was etched by using a copper chloride aqueous solution in a residual manner, and copper was measured at a tensile speed of 200 mm/min at 25 ° C, 65% RH using Tensilon of Toyo Baldwin Co., Ltd. at 25 ° C, 65% RH. The 90 degree peel strength of the foil and polyamidoximine resin. (3) Adhesion force to the wafer The polyamidoximine resin solution was applied to the mirror side of the tantalum wafer, and dried and heat-treated by the same conditions as those for the copper foil. The 5 mm width score was placed on the polyimide film side, and the peel strength was measured at a tensile speed of 200 mm/min at 25 ° C and 65% RH using a Tensilon from Toyo Baldwin. (4) Charging/discharging efficiency and cycle durability For each of the batteries fabricated in the examples, a charge and discharge test was carried out at C 2 C to determine the charge and discharge efficiency at the time of the first and repeated 30 times. Charging and discharging efficiency = [(discharge capacity / charging capacity) xl 〇〇 (%)] (synthesis of polyamido ruthenium amide resin A) in a 4-neck flask equipped with a condensing tube and a nitrogen inlet, to make a solid concentration 20% by weight of 1 mol of diphenylmethane-4,4'-diisocyanate (MDI), 0.025 mol of X-22-1660B3 (Shin-Etsu Chemical Co., Ltd., diaminopropyl Phenylmethyl polyoxane, weight average molecular weight: 4400), 氟化·〇1 molar potassium fluoride and N-methyl-2-pyrrolidone (NMP) — hydrazine, stirred at room temperature After reacting for about 1 hour, 0.975 mol of trimellitic anhydride (TM A ) was added to NMP in a manner such that the solid content concentration was 2% by weight, and 120 ° C for 2 hours and 150 ° C were added. /5 hour response. 5 -17- 201136009 Thereafter, NMP dilution was carried out so that the solid content concentration was 15% by weight. The obtained polyamidoximine resin A had a hafnoid-containing content of 24% by weight and a logarithmic viscosity of 0.72 dl/g. (Synthesis of Polyamide Amine Resin B) Using the same method as in the case of the above-mentioned polyamidoximine resin A, 0.95 moles of TMA was obtained in such a manner that the solid concentration became 2% by weight. 0.05 mol of polytetramethylene glycol (PTG) having a weight average molecular weight of 850, 0.8 mol of o-toluidine diisocyanate, 0.2 mol of 2,4-benzylidene diisocyanate, 〇.〇1 Mo Potassium fluoride and NMP in the ear are fed together, and after stirring, the reaction is carried out for 6 〇 ° C / l hour, l 2 ° ° C / 5 hours, and then the solid concentration is 15 weight while cooling. % way to benefit NMP dilution. The obtained polyamidoximine resin B had a PTG content of u s % and a logarithmic viscosity of 1.24 dl / g. (Synthesis of Polyamide Amine Resin C) 0.975 mol of TM A, 0.025 mol, in a 4-neck flask equipped with a condenser and a nitrogen inlet, and the solid concentration was 20% by weight. The terminal carboxyl group acrylonitrile-butadiene (manufactured by PTIJap an, CTBN 1300x13, weight average molecular weight: 3500), 1 molar MDI, 0.01 molar potassium fluoride and NMP-rhenium were fed to 120 After the reaction at ° C / 1.5 hours and 180 ° C for 5 hours, it was diluted with NMP while cooling and the solid content was 15% by weight. The obtained polyamidoximine resin C had a CTBN 1300x13 content of 20% by weight and a logarithmic viscosity of 1_2 〇 dl/g. (Synthesis of Polyamide Amine Resin D) In a 4-neck flask equipped with a condenser and a nitrogen inlet, the solid concentration of -18 * 201136009 is 20% by weight to add 0.95 mole of TMA and KF6003. (Study of industrial (stock) system, 〇·〇1 molar dihydroxypropyl dimethyl polyfluorene oxychloride: 22 mg KOH / g), weight average molecular weight of 8 50 0.04 Molar 3 1 Mo MDI, 0.01 The potassium fluoride of Mohr and NMP-倂 were subjected to a reaction of 6 ° C / l hour, l 2 ° ° C / 2 hours, l5 ° ° C / 5 hours, and the solid concentration was 15% by weight. The polydecylamine imide resin D obtained by the method of NMP has a decane content of 11.8 by weight of PTG of 8.0% by weight and a logarithmic viscosity of 0.98 dl/g. (Synthesis of Polyamide Amine Resin E) In a 4-neck flask equipped with a condenser and a nitrogen inlet, 1 mol of TMA, 0.0015 KF6003, and a molecular weight of 850 were obtained in such a manner that the solid content was 20% by weight. 0.0005 Mohr PTG, 1 mol of 0.01 mol of potassium fluoride and NMP-倂 are fed, and after 60 ° c / l 120 ° C / 2 h, 150 ° C / 5 h reaction, cooling The NMP was diluted by a method in which the concentration of the substance was 15% by weight. The obtained oximeimine resin E had a decane content of 0.19% by weight, 0.12% by weight of PTG, and a logarithmic viscosity of 1.02 dl/g. (Synthesis of Polyamide Amine Resin F) In a 4-neck flask equipped with a condenser and a nitrogen inlet, the solid content was 20% by weight to give 0.65 mole of TMA, 0_05 KF 6003, and a molecular weight of 850. 0.35 mole of PTG, 1 mole of 〇. 〇 1 molar potassium fluoride and NMP 倂 进 feed, 60 〆 1 l2 〇 ° C / 2 hours, i50 ° C / 5 hours reaction Thereafter, it was diluted with NMP while being cooled and the side material concentration was 15% by weight. The Shin-Etsu Chemicals Institute, OH:PTG, and materials were obtained and diluted by cooling. %, concentration of MDI, hour, the concentration of solid polythene is the concentration of MDI, hour, the convergence of solids
S -19- 201136009 胺醯亞胺樹脂F的矽氧烷含量爲30.7重量％、PTG之含量爲 34重量％、對數黏度爲0.68 dl/g。 (鋰離子二次電池負極之製造例一實施例1、2、3、4、5、 6 ) 以聚醯胺醯亞胺樹脂：負極活性物質：導電劑=7: 91: 2 之重量比率來將在上述所合成的聚醯胺醯亞胺樹脂A' B、C' D、E、F之各個浸漬液、由Si粉末（Aldrich公司製、325mesh) 所構成的負極活性物質、作爲導電劑之Ketjen碳黑與NMP — 倂利用球磨機進行混合，製造固形物濃度爲40重量％之負極 組合劑漿體，在寬度爲5.1 cm '厚度爲178 //m之銅箔上，使 乾燥膜厚成爲90 //m的方式來塗布此漿體，於150°C乾燥10 分鐘而製得鋰離子二次電池用負極。 (鋰離子二次電池用負極之製造例一實施例7、8、9) 以聚醯胺醯亞胺樹脂：負極活性物質：導電劑=5 : 92 : 3 之重量比率來將在上述所合成的聚醯胺醯亞胺樹脂 A、B、C 之各個浸漬液、由Sn粉末所構成的負極活性物質、作爲導電 劑之Ketjen碳黑與NMP —倂利用球磨機進行混合，製造固形 物濃度爲40重量％之負極組合劑漿體，在寬度爲5.1 cm、厚 度爲178 之銅箔上，使乾燥膜厚成爲90 //m的方式來塗布 此漿體，於15CTC乾燥10分鐘而製得鋰離子二次電池用負極。 (鋰離子二次電池用正極之製造例） 使PVDF :正極活性物質：導電劑=7: 91: 2之重量比率 來將作爲黏著樹脂之聚偏氟乙烯（PVDF )、作爲正極活性物 質之琥珀酸鋰、作爲導電劑之Ketjen碳黑與NMP —倂利用球 5 -20- 201136009 磨機進行混合’製造固形物濃度爲40重量％之正極組合劑 體，在寬度爲4.9 cm、厚度爲147 //m之鋁箔上，使乾燥膜 成爲90//m的方式來塗布此漿體，於150 °C乾燥1〇分鐘而作 鋰離子二次電池用正極。 (鋰離子二次電池之作成例） 將在該製造例所示之各負極、注入使1.0莫耳之LiPF6 解於乙二醇碳酸酯與二乙基碳酸酯之3: 7體積比的溶劑中 電解液的聚乙烯製多孔膜分隔膜、與在該製造例所示之正極 疊而注入箱中，製作鋰離子二次電池，將評估特性顯示於表 (比較例1 ) 使用 Solvay Advanced Polymer 公司製之 Torlon 4000T( 數黏度：ο.5 〇 dl/g)作爲聚醯胺醯亞胺樹脂且利用與實施例 同的方法而製作鋰離子二次電池負極，將評估特性之結果顯 於表1。 (比較例2 ) 使用使固形物濃度成爲15重量％的方式來將聚偏氟乙 樹脂（（股）Kureha製、KF1100)溶解於NM?之溶液，利 與實施例相同的方法而製作鋰離子二次電池負極，將評估特 之結果顯示於表1。 (比較例3 ) 使用與合成聚醯胺醯亞胺樹脂A相同的裝置，使固形物 度成爲20重量％的方式來將0.025莫耳之X-22-1660B、0. 莫耳之TMA與NMP —併進行進料，於50°C使其攪拌反應3 時後，添加50 ml之甲苯後升溫至160 °C，使其回流2小時 漿 厚 成 溶 之 重 1 ° 對 相 示 烯 用 性 濃 05 小 而 -21- 201136009 去除水。其後，使固形物濃度成爲2〇重量％的方式來進料〇.975 莫耳之TMA、1莫耳之MDI、〇.〇1莫耳之氟化鉀，於12(TC使 其反應2小時後，進一步於150 °C使其反應3小時。之後，一 邊進行冷卻且一邊使固形物濃度成爲15重量％的方式來利用 NMP進行稀釋。所獲得之聚醯胺醯亞胺樹脂〇係使用與聚醯 胺酿亞胺樹脂A相同的原料，變更製造順序，對數黏度爲〇74 dl/g'含砂氧院之含量爲24重量％。使用聚醯胺醯亞胺樹脂G， 製作與實施例同樣的電池’將評估特性之結果顯示於表1。 〔表1〕 緊貼力 (g/mm ) 充放電效率 (% ) 對銅箔 _對矽晶圓 初期値 3 〇次循環後 實施例 1 45 44 92 9 1 實施例 2 12 50 9 1 8 8 實施例3 40 18 93 8 9 實施例 4 3 3 3 8 94 92 實施例5 40 16 92 90 實施例 6 5 5 5 7 93 8 7 實施例7 45 44 94 89 實施例8 12 5 0 9 1 8 7 實施例 9 40 18 92 90 比較例 1 8 1 80 63 比較例 2 5 8 51以下 5〇以下 比較例3 25 4 8 8 50以下 應認爲此次所介紹的實施形態及實施例係全部觀點爲說 -22- 201136009 例且無限制。本發明之範圍並非上述之說明而是根據申請專利 範圍所示，謀求包含與申請專利範圍均等之意義及在範圍內之 全部的變更。 【圖式簡單說明】 〇 【主要元件符號說明】 4fff 〇S -19- 201136009 Amidoximine resin F has a decane content of 30.7 wt%, a PTG content of 34 wt%, and a logarithmic viscosity of 0.68 dl/g. (Production Example 1 of the lithium ion secondary battery negative electrode, Examples 1, 2, 3, 4, 5, 6) The weight ratio of the polyamidoquinone imide resin: negative electrode active material: conductive agent = 7: 91: 2 Each of the immersion liquids of the polyamidoximine resins A' B, C' D, E, and F synthesized as described above, and a negative electrode active material composed of Si powder (manufactured by Aldrich Co., Ltd., 325 mesh) as a conductive agent Ketjen carbon black and NMP - 混合 were mixed by a ball mill to produce a slurry of a negative electrode composition having a solid concentration of 40% by weight, and a dry film thickness of 90 on a copper foil having a width of 5.1 cm and a thickness of 178 //m. The slurry was applied in a manner of //m, and dried at 150 ° C for 10 minutes to obtain a negative electrode for a lithium ion secondary battery. (Production Example 1 of Examples for the Negative Electrode for Lithium Ion Secondary Batteries, Examples 7, 8, and 9) The above-mentioned synthesis was carried out at a weight ratio of polyamine amide imine resin: negative electrode active material: conductive agent = 5:92:3. Each of the polyacrylamide imine resin A, B, and C immersion liquids, the negative electrode active material composed of the Sn powder, and the Ketjen carbon black as a conductive agent and NMP-倂 are mixed by a ball mill to produce a solid concentration of 40. The weight % of the negative electrode assembly slurry was applied to a copper foil having a width of 5.1 cm and a thickness of 178 to a dry film thickness of 90 //m, and dried at 15 CTC for 10 minutes to obtain a lithium ion. A negative electrode for a secondary battery. (Production Example of Positive Electrode for Lithium Ion Secondary Battery) PVDF: Positive Electrode Active Material: Conductive Agent = 7:91:2 by weight ratio, polyvinylidene fluoride (PVDF) as an adhesive resin, and amber as a positive electrode active material Lithium acid, Ketjen carbon black as a conductive agent, and NMP-倂 were mixed by a ball 5-20-201136009 mill to produce a positive electrode assembly body having a solid concentration of 40% by weight, having a width of 4.9 cm and a thickness of 147 / On the aluminum foil of /m, the slurry was applied so that the dried film became 90/m, and dried at 150 ° C for 1 minute to serve as a positive electrode for a lithium ion secondary battery. (Example of Lithium Ion Secondary Battery) Each of the negative electrodes shown in the production example was injected with 1.0 mol of LiPF6 in a solvent of 3:7 by volume ratio of ethylene carbonate to diethyl carbonate. A polyethylene porous membrane separator film of the electrolytic solution was placed in a tank and placed in a tank, and a lithium ion secondary battery was produced. The evaluation characteristics are shown in the table (Comparative Example 1), manufactured by Solvay Advanced Polymer Co., Ltd. Torlon 4000T (number viscosity: ο. 5 〇 dl / g) was used as a polyamidoximine resin, and a lithium ion secondary battery negative electrode was produced by the same method as the example. The results of evaluation characteristics are shown in Table 1. (Comparative Example 2) A solution in which a polyvinylidene fluoride resin (manufactured by Kureha Co., Ltd., KF1100) was dissolved in NM? was used to have a solid content of 15% by weight, and lithium ions were produced in the same manner as in the examples. The secondary battery negative electrode, the results of the evaluation are shown in Table 1. (Comparative Example 3) Using the same apparatus as the synthetic polyamidoximine resin A, the solid content was 20% by weight, and 0.025 mol of X-22-1660B, 0. Mole TMA and NMP were used. - The feed is further carried out, and after stirring at 50 ° C for 3 hours, 50 ml of toluene is added, and the temperature is raised to 160 ° C, and the mixture is refluxed for 2 hours. The slurry is dissolved to a weight of 1 °. 05 Small and -21-201136009 Remove water. Thereafter, 〇.975 Molar TMA, 1 Moule MDI, 〇.〇1 Molar potassium fluoride was fed in such a manner that the solid content concentration was 2% by weight, and 12 (TC made the reaction 2) After the lapse of the reaction, the reaction was further carried out for 3 hours at 150 ° C. Thereafter, the mixture was diluted with NMP while cooling to a solid concentration of 15% by weight. The obtained polyamidoximine resin was used. The same raw material as that of the polyamide amine-imide resin A was changed in the order of production, and the logarithmic viscosity was 〇74 dl/g, and the content of the sand-containing oxygen chamber was 24% by weight. The polyamine amide imine resin G was used for production and implementation. For the same battery, the results of the evaluation characteristics are shown in Table 1. [Table 1] Adhesion force (g/mm) Charge and discharge efficiency (%) Example of copper foil _ 矽 wafer initial 値 3 cycles 1 45 44 92 9 1 Example 2 12 50 9 1 8 8 Example 3 40 18 93 8 9 Example 4 3 3 3 8 94 92 Example 5 40 16 92 90 Example 6 5 5 5 7 93 8 7 Implementation Example 7 45 44 94 89 Example 8 12 5 0 9 1 8 7 Example 9 40 18 92 90 Comparative Example 1 8 1 80 63 Comparative Example 2 5 8 51 or less 5〇 Next Comparative Example 3 25 4 8 8 50 The following is to say that the embodiments and examples described herein are all examples of -22-201136009 and are not limited. The scope of the present invention is not the above description but based on the patent application. In the scope of the application, it is intended to include all modifications within the scope and scope of the patent application. [Simple description of the diagram] 〇 [Main component symbol description] 4fff 〇
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