200401464 (1) 玖、發明說明 【發明所屬之技術領域】 本發明有關一種鋰二次電池及其製造。 【先前技術】 電池是一種經由電化學反應將化學物質之化學能轉換 成電能之裝置，分成兩類：一次電池及二次電池。在可充 電之二次電池中，鋰二次電池最重要，因其於現存電池中 具有最高之電壓及最大之能量密度。該鋰二次電池係根據 所使用之電解質分成三種：使用液體電解質之液體型電 池；使用混合有聚合物及液體之凝膠電解質的凝型電 池；及使用固體電解質之固體型電池。 美國專利編號5,460,904揭示一種製造鋰二次電池之 方法。該專利之電池係如下製得：將包含分散於聚合物黏 合劑基質中之可插入材料的負極膜舖置於開放網柵形式之 陽極收集箔上。經塑化之電解質/隔板膜係放置於該負極 膜上’且覆上正極膜’其包含位於聚合物黏合劑基質中之 細粉狀鋰插入化合物組成物。鋁收集箔或柵完成該組合 體’其隨之於加熱及壓力下壓於台板之間，以軟化且黏合 該聚合物組件’且層積該膜及柵層。所得之層積物隨之依 鋸齒方式摺疊’得到多槽件電池。然而，該方法易產生缺 點爲電極係串聯’當層積物於鋸齒形下摺疊時，電極經常 受損。此外’該方法需於製備塑化隔板時添加增塑劑，且 以溶劑萃取增塑劑。此外，陽極與陰極之間經常發生短 (2) (2)200401464 路，因其難以於層積過程中均勻地層積。是故，該方法未 普遍使用於鋰二次電池之大規模製備。 美國專利編號5,8 3 7,0 1 5揭示一種聚合物電池，其中 使用多層聚合物膜作爲隔板。該多層聚合物膜係藉著於習 用疏電解質性聚合物膜諸如聚乙烯膜之兩表面上塗覆對於 電解質具有親和性之聚合物（例如，聚偏二氟乙烯）而製 得。該聚合物電池中，習用隔板係由作爲隔板之多層聚合 物膜取代。該多層聚合物膜對於電極之黏合係藉由加熱該 電極及多層聚合物膜至足以使該聚合物凝膠化，以黏合該 電極之溫度。此種技術較習用方法重要，因爲不需要使用 溶劑萃取，可使用目前用於製造鋰離子電池之設備。然 而，該方法具有該電化學電池之內電阻劇幅增加的缺點， 因爲對於電解質具有親和性之聚合物與具有疏電解質特性 之聚乙烯之間的離子傳導差。 KR 3 0 9,904揭示一種鋰二次電池，其包含一隔板、 多片陰極板及多片陽極板，其中該陰極板係依預定次序黏 著於隔板之一側面上，而多片陽極板係黏著於隔板之另一 側面，使得各陰極板與各陽極板彼此相對，而隔板具有鋸 齒形式。然而，該鋰二次電池缺點爲難以緊緊地固定該隔 板’因爲隔板之摺疊係依鋸齒方式進行。於電極與隔板間 產生一間隙，破壞了電化學電池之週期壽命。此外，該陽 極板及陰極板應排列於該隔板之相對側面，使得黏著過程 複雜化。此外，因爲依鋸齒方式進行摺疊，而非固定一方 向方式，故該摺疊方法更爲複雜。是故’無法大量製造此 (3) (3)200401464 等錐—次電池。 【發明內容】 因此’本發明之目的係提供一種製造鋰二次電池之方 法，其與習用電池比較之下，具有改良之產能、高產率、 較長之週期壽命及較高之充電-放電特性。 本發明另一目的係提供一種具有新穎結構之鋰二次電 池。 本發明另一目的係提供一種可簡易地製造具有各種形 狀及容量之電池的方法。 本發明鋰二次電池包含多片陰極板及多片陽極板，其 中各陰極及陽極板係具有一分接頭、一隔板一此隔板之一 側面上塗覆有離子-傳導性聚合物材料、及一電解質，其 中各陰極板及各陽極板係彼此交錯且並聯，該陰極板及陽 極板之分接頭個別重疊，該交錯之陰極及陽極板係藉具有 ~~^二.I j Ι^ΐ 或 11^^ 5 ’之結構的隔板分隔，且電解質係放置於藉 隔板分隔之各陰極與各陽極之間。本發明鋰二次電池簡化 了摺疊程序及黏著程序。該電池可藉著於固定單一方向摺 疊該隔板而製備，以簡化該摺疊，而該電極板係僅黏著於 該隔板之一表面，以簡化該電極板對該隔板之黏著一其係 與KR 309,604之鋰二次電池比較。 圖1出示本發明所使用具有分接頭之電極板的較佳實 施例。該電極板】009包括陰極板及陽極板）係藉著於電流 集極1 0]之兩表面上塗覆含有電極活性材料之溶液，以形 (4) (4)200401464 成電極活性材料之塗層1 0 2，之後將經塗覆之電流集極 1 〇 1裁成適當之大小而製備。該電極板1 〇〇—不構成限 制一可裁成矩形或圓形，其先決條件爲該電極板1 〇〇具有 分接頭1 0 3。該電極板1 0 0之形狀可根據最終電化學電池 所需形式而改變。即，具有所需形狀之電極板1 00可藉著 將切割機或打孔機之模板調成適當之形狀而大量生產。塗 覆於電流集極1 0 1表面上之電極活性材料（陰極活性材料 及陽極活性材料）不特別限制。可廣泛使用在鋰二次電池 中作爲電極活性材料之材料。較佳陰極及陽極活性材料係 例示於美國專利序號 5,837,015、5,635,151及5,501,548 中。詳言之，陽極活性材料可提及可插入/取出 (deintercalation)鋰離子之材料，諸如鋰金屬、鋰合金、 碳及石墨。該陽極活性材料以碳或石墨爲佳。該陰極活性 於插入/取出反應期間具有高電化學電位，而陽極活性材 料則具有低電化學電位。 該陰極或陽極材料係分散於適當之溶劑中，塗覆於電 流集極1 〇 1表面上’裁成所需大小，以個別形成陰極或陽 極板。該電極活性材料可塗覆於電流集極之一表面上。以 塗覆於該電流集極101之兩表面爲佳，如圖1所示。雙面 塗覆使得每單位體積之放電容量增加。電流集極1 〇 1之較 佳實例請參照美國專利序號5，8 3 7，0 1 5、5，6 3 5，1 5 1及 5,501，548’其以提及方式倂入本文中。根據本發明特定 實施例’個別使用鋁薄板及銅薄板作爲陰極及陽極電流集 極。其間’該電極活性材料通常係塗覆於電流集極1 〇1表 (5) (5)200401464 面上’同時結合使用增加電化學電池之電導係數之電流傳 導性材料’及同時將電極活性材料及電流傳導性材料黏著 於電流集極1 0 1之黏合劑。根據本發明有關之熟習此項技 術者所熟知的電極活性材料，可輕易選擇電流傳導性材料 及黏合劑之選擇。 防止陰極與陽極直接電接觸且提供離子通過使用之孔 的隔板’可爲數種技術界已知材料中之任一種。較佳實例 有多孔性聚烯烴薄膜，諸如聚乙烯膜或聚丙烯膜，多孔性 聚偏二氟乙烯膜，多孔性六伸丙基氟薄膜及多孔性聚氧化 乙烯膜。該聚乙烯膜係廣泛使用於技術界。該隔板可包含 兩層或多層多孔性薄膜。塗覆於隔板之一側面上的離子傳 導性聚合物將電極板固定且黏合於隔板上，且可爲與其他 電池組件具有電化學相容性、於充電/放電反應期間具有 安定性且具有離子傳導性之數種材料中的任一種。就離子 傳導性聚合物材料而言，可提及聚氧化丙烯、聚胺基甲酸 酯、聚甲基丙烯酸甲酯、聚甲基丙烯酸丁酯、聚氰基丙烯 酸酯' 聚乙烯丙烯酸、聚丙烯腈、聚偏二氟乙烯、聚六伸 丙基氟、聚氧化乙烯、或其混合物。該離子傳導性聚合物 材料係溶解於適當之溶劑中，之後藉習用技術塗覆於該隔 板之一側面上。就用以溶解該離子傳導性聚合物材料之溶 劑而言，可提及碳酸二甲酯、乙腈、四氫呋喃、丙酮及甲 基乙基酮。根據本發明較佳實施例，藉者將0.5至1 〇重 量份數離子傳導性聚合物材料溶解於溶劑中所製備之聚合 物溶液係於〗至20微米厚度下塗覆於隔板之一側面上。 (6) 200401464 離子傳導性聚合物之用量低於0 _ 5重量份數時，無法達到 充分黏著性。當離子傳導性聚合物用量超過1 0重量份數 時，該電解質之離子移動性受損。 就電解質而言，可使用液體電解質、凝膠電解質或固 體電解質。根據本發明較佳實施例，使用藉著將鋰鹽諸如200401464 (1) 发明. Description of the invention [Technical field to which the invention belongs] The present invention relates to a lithium secondary battery and its manufacture. [Previous Technology] A battery is a device that converts chemical energy of a chemical substance into electrical energy through an electrochemical reaction. It is divided into two categories: primary batteries and secondary batteries. Among the rechargeable secondary batteries, lithium secondary batteries are the most important because they have the highest voltage and the highest energy density among existing batteries. The lithium secondary battery is divided into three types according to the electrolyte used: a liquid type battery using a liquid electrolyte; a coagulation type battery using a polymer and a liquid gel electrolyte; and a solid type battery using a solid electrolyte. U.S. Patent No. 5,460,904 discloses a method for manufacturing a lithium secondary battery. The battery of this patent is prepared by laying a negative electrode film containing an insertable material dispersed in a polymer binder matrix on an anode collecting foil in the form of an open grid. A plasticized electrolyte / separator film is placed on the negative electrode film and is covered with a positive electrode film 'which contains a fine powdery lithium intercalation compound composition in a polymer binder matrix. The aluminum collection foil or grid completes the assembly ′ which is then pressed between the platens under heat and pressure to soften and adhere the polymer component ’and laminate the film and grid. The resulting laminate is then folded in a zigzag manner 'to obtain a multi-slot battery. However, this method is prone to the disadvantage that the electrode system is connected in series. When the laminate is folded under the zigzag shape, the electrode is often damaged. In addition, this method requires adding a plasticizer when preparing a plasticized separator, and extracting the plasticizer with a solvent. In addition, short (2) (2) 200401464 paths often occur between the anode and cathode because it is difficult to uniformly laminate during the lamination process. Therefore, this method is not widely used for large-scale production of lithium secondary batteries. U.S. Patent No. 5,8 3 7,0 1 5 discloses a polymer battery in which a multilayer polymer film is used as a separator. The multilayer polymer film is prepared by coating a polymer having an affinity for an electrolyte (for example, polyvinylidene fluoride) on both surfaces of a conventional electrolyte-repellent polymer film such as a polyethylene film. In this polymer battery, a conventional separator is replaced by a multilayer polymer film as a separator. The adhesion of the multilayer polymer film to the electrode is achieved by heating the electrode and the multilayer polymer film to a temperature sufficient to gel the polymer to adhere the electrode. This technique is more important than the conventional method because it does not require solvent extraction and can be used with equipment currently used to make lithium-ion batteries. However, this method has the disadvantage of a sharp increase in the resistance within the electrochemical cell because of the poor ion conductivity between the polymer having affinity for the electrolyte and the polyethylene having electrolyte-repellent properties. KR 3 0 9,904 discloses a lithium secondary battery including a separator, a plurality of cathode plates, and a plurality of anode plates, wherein the cathode plate is adhered to one side of the separator in a predetermined order, and the plurality of anode plates are Adhere to the other side of the separator so that each cathode plate and each anode plate are opposite each other, and the separator has a zigzag form. However, the lithium secondary battery has the disadvantage that it is difficult to hold the separator tightly because the folding of the separator is performed in a zigzag manner. A gap is created between the electrode and the separator, which destroys the cycle life of the electrochemical cell. In addition, the anode and cathode plates should be arranged on opposite sides of the separator, which complicates the adhesion process. In addition, the folding method is more complicated because it is folded in a zigzag manner instead of a fixed one-way manner. That ’s why it ’s impossible to mass-produce this (3) (3) 200401464 etc. cone-secondary battery. [Summary of the Invention] Therefore, the object of the present invention is to provide a method for manufacturing a lithium secondary battery, which has improved productivity, high yield, longer cycle life, and higher charge-discharge characteristics compared with conventional batteries. . Another object of the present invention is to provide a lithium secondary battery having a novel structure. Another object of the present invention is to provide a method for easily manufacturing batteries having various shapes and capacities. The lithium secondary battery of the present invention includes multiple cathode plates and multiple anode plates, wherein each cathode and anode plate has a tap, a separator, and one side of the separator is coated with an ion-conductive polymer material, And an electrolyte, in which each cathode plate and each anode plate are staggered and connected in parallel with each other, and the taps of the cathode plate and the anode plate are individually overlapped, and the staggered cathode and anode plates have ~~ ^ 二 .I j Ι ^ ΐ Or 11 ^^ 5 'structured separator, and the electrolyte is placed between each cathode and each anode separated by the separator. The lithium secondary battery of the present invention simplifies the folding process and the adhesion process. The battery can be prepared by folding the separator in a fixed single direction to simplify the folding, and the electrode plate is only adhered to one surface of the separator to simplify the adhesion of the electrode plate to the separator. Compared with KR 309,604 lithium secondary battery. Fig. 1 shows a preferred embodiment of an electrode plate having a tap used in the present invention. The electrode plate] 009 includes a cathode plate and an anode plate) is formed by coating a solution containing an electrode active material on both surfaces of the current collector 10], and forming a coating of the electrode active material in the shape of (4) (4) 200401464. 102, and then the coated current collector 101 was cut to an appropriate size and prepared. The electrode plate 100 does not constitute a limitation, and can be cut into a rectangle or a circle. The prerequisite is that the electrode plate 100 has a tap 103. The shape of the electrode plate 100 can be changed according to the desired form of the final electrochemical cell. That is, an electrode plate 100 having a desired shape can be mass-produced by adjusting a template of a cutting machine or a punch into an appropriate shape. The electrode active material (cathode active material and anode active material) coated on the surface of the current collector 101 is not particularly limited. It can be widely used as a material for electrode active materials in lithium secondary batteries. Preferred cathode and anode active materials are exemplified in U.S. Patent Nos. 5,837,015, 5,635,151, and 5,501,548. In detail, the anode active material may be a material capable of inserting / deintercalating lithium ions, such as lithium metal, lithium alloy, carbon, and graphite. The anode active material is preferably carbon or graphite. The cathode has a high electrochemical potential during the insertion / removal reaction, while the anode active material has a low electrochemical potential. The cathode or anode material is dispersed in a suitable solvent, coated on the surface of the current collector 101 'and cut to a desired size to form the cathode or anode plate individually. The electrode active material may be coated on one surface of a current collector. It is better to coat both surfaces of the current collector 101, as shown in FIG. Double-sided coating increases the discharge capacity per unit volume. For a better example of the current collector 101, please refer to U.S. Patent Nos. 5,8 3,7,0 1 5,5,6 3 5,1 5 1 and 5,501,548 'which are incorporated herein by reference. According to a specific embodiment of the present invention ', an aluminum sheet and a copper sheet are individually used as a cathode and an anode current collector. In the meantime, the electrode active material is usually coated on the surface of the current collector 1 (Table 1) (5) (5) 200401464. 'Simultaneously combined with the use of a current-conducting material that increases the conductivity of an electrochemical cell' and the electrode active material And the current-conducting material is adhered to the adhesive of the current collector 101. According to the electrode active material familiar to those skilled in the art who are familiar with the present invention, the choice of the current conductive material and the binder can be easily selected. A separator ' which prevents direct electrical contact between the cathode and anode and provides pores through which ions can pass can be any of several materials known in the art. Preferred examples are porous polyolefin films, such as polyethylene or polypropylene films, porous polyvinylidene fluoride films, porous hexapropylene films, and porous polyethylene oxide films. This polyethylene film is widely used in the technical field. The separator may include two or more porous films. An ion-conducting polymer coated on one side of the separator fixes and adheres the electrode plate to the separator, and may have electrochemical compatibility with other battery components, stability during charge / discharge reactions, and Any of several materials with ion conductivity. As far as ion conductive polymer materials are concerned, mention may be made of polyoxypropylene, polyurethane, polymethylmethacrylate, polybutylmethacrylate, polycyanoacrylate 'polyethylene acrylic, polypropylene Nitrile, polyvinylidene fluoride, polyhexamethylene fluoride, polyethylene oxide, or a mixture thereof. The ion-conducting polymer material is dissolved in a suitable solvent, and then applied to one side of the separator by conventional techniques. As a solvent for dissolving the ion conductive polymer material, dimethyl carbonate, acetonitrile, tetrahydrofuran, acetone, and methyl ethyl ketone can be mentioned. According to a preferred embodiment of the present invention, a polymer solution prepared by dissolving 0.5 to 10 parts by weight of an ion-conducting polymer material in a solvent is applied on one side of the separator at a thickness of ≧ 20 μm. . (6) 200401464 When the amount of the ion conductive polymer is less than 0 to 5 parts by weight, sufficient adhesion cannot be achieved. When the amount of the ion conductive polymer exceeds 10 parts by weight, the ion mobility of the electrolyte is impaired. As the electrolyte, a liquid electrolyte, a gel electrolyte, or a solid electrolyte can be used. According to a preferred embodiment of the present invention, a lithium salt such as
LiCF3S03、Li(CF3S02)2、LiPF6 ' LiBF4、LiCl〇4 或LiCF3S03, Li (CF3S02) 2, LiPF6 'LiBF4, LiCl〇4 or
LiN(S02C2F5)2溶解於極性有機溶劑諸如碳酸乙二g旨、LiN (S02C2F5) 2 is dissolved in a polar organic solvent such as ethylene carbonate,
碳酸丙二醇酯、碳酸二甲酯、碳酸二乙酯及碳酸甲醋乙酯 中所製備之液體電解質溶液。 本發明另外提供一種製造鋰二次電池之方法，其包 含： a)於隔板之一側面上塗覆離子傳導性聚合物材料；匕) 依預定順序將多片陰極板及陽極板排列於隔板塗覆有離子 傳導性聚合物材料之表面上，以藉連續摺疊製備堆疊體， 其中各陰極板及各陽極板係彼此交錯且並聯，陰極板及陽 極板之分接頭個別重疊’交錯之陰極及陽極板係藉由具有A liquid electrolyte solution prepared in propylene carbonate, dimethyl carbonate, diethyl carbonate, and ethyl methyl carbonate. The present invention further provides a method for manufacturing a lithium secondary battery, comprising: a) coating an ion conductive polymer material on one side of a separator; d) arranging a plurality of cathode plates and anode plates on the separator in a predetermined order On the surface coated with ion-conducting polymer material, a stacked body is prepared by continuous folding, wherein each cathode plate and each anode plate are staggered and connected in parallel, and the taps of the cathode plate and the anode plate are individually overlapped. The anode plate is
結構之隔板分隔；c)將隔板連續摺囊，以 得到堆疊體；及d)將所得之堆疊體放置於一封裝物內， 之後注射電解質溶液且封裝。 離子傳導性聚合物材料於隔板之一側面上的塗覆係藉 著於隔板之一表面上噴灑或塗糊將離子傳導性聚合物材料 洛解於適當之有機ί谷劑中的聚合物溶液而達成。 在塗覆離子傳導性聚合物材料之隔板表面上，排列多 片陰極板及多片陽極板。該陰極板及陽極板之排列順序不 (7) (7)200401464 特別限制，其先決條件爲完成連續摺疊時，得到一堆疊 體，其中各陰極板及各陽極板係彼此交錯且並聯，陰極板 及陽極板之分接頭個別重疊，而交錯之陰極與陽極板係藉 隔板分隔。該電極板之排列順序係使一陽極板（或一陰極 板）排列於隔板末端，兩相鄰陰極板及兩相鄰陽極板係排 列於隔板中間，而於該陰極板與該陽極板之間適當地形成 利用空間爲佳。 圖2 a至2 c出示配置於隔板之一側面上的多片陰極及 陽極之較佳配置。如圖2a至2c所示，多片陰極板202a 至2 02以總稱爲”202”）、多片陽極板203 a至2 03 f(總稱爲 2 03 )係配置於隔板201之單一側面上，適當地於該陰極板 202與陽極板203之間形成利用空間。在進續摺疊時，沿 著完成之摺疊線204 —於兩電極板之間及於電極板與利用 空間之間形成，得到一堆疊體，其中各陰極板203及各陽 極板202係彼此交錯且並聯，且陰極板202及陽極板203 之分接頭個別重疊。 詳言之，圖2a出示一例示配置，其中陰極板202及 陽極板203係排列於隔板20 1之一側面上，順序爲陽極板 2 0 3 a/利用空氣/陰極板202a/陰極板202b/陽極板2 03 b/陽 極板203 c/…/陰極板202c/陰極板2 02d/陽極板203 d/陽極 板203 e/陰極板202e/利用空間/陽極板203 f/利用空間。沿 摺疊線204連續摺疊，得到圖3及4所示之堆疊體，其中 各陰極板202係與各陽極板203交錯，且陰極板202與陽 極板203之分接頭個別重疊。所得堆疊體係放置於適當之 (8) 200401464 封裝物內，之後注射電解質溶液且封裝，產生本發明電 池。該方法具有可依簡單方法製造電池之優點。The structure is separated by a separator; c) the separator is continuously folded to obtain a stack; and d) the obtained stack is placed in a package, and then an electrolyte solution is injected and sealed. The application of the ion conductive polymer material on one side of the separator is to spray or paste on one surface of the separator to dissolve the ion conductive polymer material in a polymer in a suitable organic cereal. Solution. On the surface of the separator coated with the ion conductive polymer material, a plurality of cathode plates and a plurality of anode plates are arranged. The arrangement order of the cathode plate and the anode plate is not particularly limited. (7) (7) 200401464 The prerequisite is that when a continuous folding is completed, a stack is obtained, in which each cathode plate and each anode plate are staggered and connected in parallel, and the cathode plate The anode and the anode plate are individually overlapped, and the staggered cathode and anode plate are separated by a separator. The arrangement of the electrode plates is such that an anode plate (or a cathode plate) is arranged at the end of the separator, two adjacent cathode plates and two adjacent anode plates are arranged in the middle of the separator, and the cathode plate and the anode plate are arranged It is better to form a proper use space between them. Figures 2a to 2c show a preferred configuration of a plurality of cathodes and anodes arranged on one side of a separator. As shown in FIGS. 2a to 2c, a plurality of cathode plates 202a to 202 are collectively referred to as “202”), and a plurality of anode plates 203a to 203f (collectively 2 03) are arranged on a single side of the separator 201. An appropriate use space is formed between the cathode plate 202 and the anode plate 203. During further folding, it is formed along the completed folding line 204—between two electrode plates and between the electrode plates and the utilization space, to obtain a stack, in which each cathode plate 203 and each anode plate 202 are staggered with each other and In parallel, the taps of the cathode plate 202 and the anode plate 203 overlap each other. In detail, FIG. 2 a shows an exemplary configuration, in which the cathode plate 202 and the anode plate 203 are arranged on one side of the separator 20 1, in the order of anode plate 2 0 3 a / utilized air / cathode plate 202a / cathode plate 202b / Anode plate 2 03 b / Anode plate 203 c /… / Cathode plate 202c / Cathode plate 2 02d / Anode plate 203 d / Anode plate 203 e / Cathode plate 202e / Usage space / Anode plate 203 f / Usage space. Continuously folding along the fold line 204 to obtain the stacked body shown in Figs. 3 and 4, wherein each cathode plate 202 is staggered with each anode plate 203, and the taps of the cathode plate 202 and the anode plate 203 are individually overlapped. The resulting stacked system was placed in a suitable (8) 200401464 package, and then the electrolyte solution was injected and sealed to produce the battery of the present invention. This method has the advantage that the battery can be manufactured by a simple method.
圖2b出示陰極板202及陽極板203之另一較佳配 置，其中其係依陽極板203 a/利用空間/陰極板202a/陰極 板 2 02b/陽極板203b/陽極板2 03 c/…/陰極板202c/陰極 202d/陽極板203 d/陽極板203 e/利用空間之順序排列。沿 摺疊線204連續摺疊，該配置產生如同圖3之電極結構， 其中各陰極板202及各陽極板203係彼此交錯。圖2c出 示陰極板202與陽極板203之另一種配置，其中其係依陽 極板203 a/利用空間/陰極板202a/陰極板202b/陽極板 203 b/陽極板203 c/···/利用空間/利用空間/···/陰極板202c/ 陰極板202d/陽極板203 d/陽極板203 e/利用空間/陰極板 202e之順序排列。沿摺疊線204於兩方向連續摺疊，得 |i ΊFig. 2b shows another preferred configuration of the cathode plate 202 and the anode plate 203, which is based on the anode plate 203a / utilization space / cathode plate 202a / cathode plate 2 02b / anode plate 203b / anode plate 2 03 c /.../ The cathode plate 202c / cathode 202d / anode plate 203d / anode plate 203e / use space are arranged in this order. Continuously folding along the fold line 204, this configuration produces the electrode structure as shown in FIG. 3, in which each of the cathode plates 202 and each of the anode plates 203 are staggered with each other. Fig. 2c shows another configuration of the cathode plate 202 and the anode plate 203, wherein it is based on the anode plate 203a / utilization space / cathode plate 202a / cathode plate 202b / anode plate 203b / anode plate 203 c / ... The space / utilization space /.../ the cathode plate 202c / the cathode plate 202d / the anode plate 203d / the anode plate 203e / the utilization space / the cathode plate 202e are arranged in this order. Continuously fold in two directions along the fold line 204 to get | i Ί
到一堆疊體，其中隔板之結構係爲 ’因此，應已知該 陽極板及該陰極板之配置不特別限制，其先決條件爲陰極 板及陽極板兩者皆黏著於隔板之表面上，得到一堆疊體， 其中各陰極板及各陽極板係彼此交錯且並聯，陰極板及陽 極板之分接頭個別重疊，而交錯之陰極與陽極板係藉隔板 分隔。 陽極板或陰極板之數目可適當地選擇，視欲使用之陽 極活性材料、欲使用之陰極活性材料、欲使用之電解質、 及電池所需之放電能力而定。當陽極板（或陰極板）數目大 於I 00時，摺疊程序複雜。因此，陽極板使用範圍係爲1 至1〇〇。以使用1至50片陽極板爲佳，2至20更佳，而 -11 - (9) (9)200401464 4至1 5最佳。 詳細說明如下。作爲陰極活性材料之鋰-過渡金屬氧 化物一視情況結合有電流傳導性材料、黏合劑及添加劑諸 如抗氧劑及阻燃劑一分散於適當之溶劑中’之後塗覆於陰 極電流集極（例如鋁薄板）上。經塗覆之陰極電流集極經乾 燥，以輥壓機加壓，之後裁成適當之大小，產生陰極板。 相同地，陽極活性材料及黏合劑係分散於適當之溶劑中， 塗覆、乾燥、加壓且裁成適當之大小，產生陽極板。如圖 2a至2c所示，所得之陰極及陽極板係於預定順序下排列 於隔板塗覆有離子傳導性聚合物材料之一側面上。連續摺 疊排列有電極板之隔板，產生堆疊體，其中各陰極板及各 陽極板係彼此交錯，陰極板及陽極板之分接頭個別重疊以 使該陰極板及陽極板並聯，而交錯之陰極與陽極板係藉隔 板分隔。之後，將堆疊體放置於封裝物中，注射電解質溶 液，以分散且進料至陰極板與隔板之間及至該陽極板與該 隔板之間。 本發明方法之步驟係連續進行，大規模地產生鋰二次 電池。例如，步驟a)至d )可在經輥壓之隔板依適當之速 度壓出後，進續地進行。如此，因爲電極板係僅黏著於隔 板之一側面上’故黏著程序（步驟b)簡單，且產率增加。 此外，排列有電極板之隔板依固定方向摺疊，而非依鋸齒 方式’故簡化摺疊程序（步驟c)。其間，未輥壓隔板之末 端的裁切可根據操作條件而進行。即，未輥壓隔板之一末 端的裁切可於步驟a)及步驟b)之間、於步驟b)及步驟c) (10) (10)200401464 之間或於步驟C)及步驟d)之間進行。 該陰極及陽極板之分接頭個別導出至適當之引線’諸 如鋁及鎳引線，藉超音波焊接並聯。之後，藉將堆疊體裝 入一封裝物中、之後注射電解質溶液且於真空下加熱密封 該封裝物，而製得最終電池。此時，通常使用鐵或鋁作爲 封裝材料。 參照特定實施例更充分地描述本發明。然而，應已知 該實施例僅供說明，而不應限制本發明。可在不偏離本發 明範圍及精神下進行許多修飾。 【實施方式】 實施例 實施例1 :電極板之製備 陰極板係藉習用方法製備：1 〇〇克作爲陰極活性材料 之Li Co 02粉末、5克作爲電流傳導性材料之碳黑及5克 作爲黏合劑之聚偏二氟乙烯均勻混合，之後將1 0 0毫升 N -甲基吡略烷酮添加於該混合物中。所得溶液塗覆於厚度 1 5微米而作爲電流集極之鋁箔的兩側面上，乾燥且以輥 壓機加壓。陰極板之厚度係爲1 5 0微米。 相同地’製備陽極板：1 0 0克石黑粉及1 0克作爲黏 合劑之聚偏二氟乙烯均勻混合，之後將1 0 0毫升N -甲基 吡咯烷酮添加於該混合物中。所得之溶液塗覆於作爲陽極 集極而厚度1 5微米之銅箔的兩側面上，乾燥且以輥壓機 加壓。陰極板厚度係爲1 5 0微米。 -13- (11) (11)200401464 陰極及陽極板使用打孔機裁切’以得到如圖1所示之 陰極及陽極，其中各陰極及陽極板係具有分接頭。所得之 陰極板及陽極板係儲存於卡匣內。 實施例2 :電池（1)之製備 聚合物溶液係藉著於1 〇〇 : 3重量比下混合乙腈（購自 Aldrich)及聚氧化乙烯（購自 Aldrich，平均分子量 1，00 0,000)而製備。所得之聚合物溶液塗覆於多孔性聚乙 烯板之一側面上（TecklonTM, ENTEK製造，厚度：25微 米），此板係作爲液體固定輸送裝置之隔板，厚度2微 米。 來自卡匣之五片陰極板及六片陽極板依圖2所示之順 序排列於該裝置塗覆有聚合物溶液之側面上，之後沿摺疊 線連續摺疊’以形成圖3所示之堆疊體。陰極板及陽極板 突出之分接頭藉鎳及鋁引線導出，使用超音波個別平行焊 接。該堆疊體裝於具有一個可容裝堆疊體之袋的鋁層積板 內，將藉由溶解1.2莫耳LiPF6& 3毫升碳酸乙二醇酯與 碳酸乙基甲酯（1 : 1體積）混合溶劑所製備之電解質溶液注 射於該袋中。於真空下加熱密封該袋，產生厚度3 8毫 米、寬度35毫米且長度62毫米之鋰二次電池。 實施例3 :電池（2)之製備 鋰二次電池係依實施例]所述方式製備，不同處係使 用聚甲基丙烯酸甲酯取代聚氧化乙烯。 -14 - (12) (12)200401464 對照例1 依實施例2所述方式製備KR 3 09,6 04所述之鋰二次 電池’不同處係依預定順序將五片陰極板黏著於隔板塗覆 有聚氧化乙烯溶液之一側面上。之後，該聚氧化乙烯溶液 再塗覆於隔板之另一側面上，五片陽極板黏著於隔板之另 一側面上’以得到其中隔板係夾置於陰極板與陽極板之間 的配置。摺疊係依鋸齒方式進行，產生電池。 電池週期壽命之測試 測試實施例2之電池的週期壽命，與實施例1比較。 其結果係出示於圖5中。如圖5所示，本發明鋰二次電池 在4 0週期以上時，仍保留95 %或更高之放電容量，而對 照例1電池具有低於90%之放電容量。由此等結果發現， 本發明電池具有遠較對照例1改善之週期壽命特性。 如前文所述，本發明方法不需要層積程序來以高溫及 高壓將電極膜緊密黏合於隔板上。此外，其可輕易提供各 種形狀之電池，對電極板不造成任何損傷，因爲各電極板 皆於預先裁切形式下使用。與KR 3 09,640揭示之鋰二次 電池比較之下，本發明方法可簡化摺疊程序及黏著程序， 因爲電極板僅黏著於該隔板之一側面上，連續摺疊係於固 定方向上進行，而非以鋸齒方式進行。是故，本發明方法 適用於連續製造鋰二次電池，可於高產率及於改良之產能 下生產鋰二次電池。所製之鋰二次電池具有各陰極板及各 (13) (13)200401464 陽極板係穩定地藉由緊密保持於電池中之隔板分隔的優 點，而改善週期壽命特性。 【圖式簡單說明】 圖1係爲具有分接頭之電極板的透視圖，其係使用含 有電極活性材料之溶液塗覆電流集極之兩表面，且將經塗 覆之電流集極裁成適當之大小而製得。 圖2至2 C係爲出示多片位於隔板之一側面上的電極 板之本發明較佳配置的平面圖。 圖3係爲藉由連續摺疊圖2 a之配置所得的堆疊體之 剖面圖。 圖4係爲圖3之堆疊體的透視圖。 圖5係爲出示實施例2電池之週期壽命的特性圖，與 對照例1比較 ' ο 元件符號對照表 100 電極板 10 1 電流極集 102 塗層 103 分接頭 20 1 隔板 202a-202e 陰極板 2 03 a-2 03 f 陽極板 204 摺疊線To a stack, where the structure of the separator is' Therefore, it should be known that the configuration of the anode plate and the cathode plate is not particularly limited, and its prerequisite is that both the cathode plate and the anode plate are adhered to the surface of the separator A stacked body is obtained, in which each cathode plate and each anode plate are staggered and connected in parallel with each other, and the taps of the cathode plate and the anode plate are individually overlapped, and the staggered cathode and the anode plate are separated by a separator. The number of anode plates or cathode plates may be appropriately selected depending on the anode active material to be used, the cathode active material to be used, the electrolyte to be used, and the discharge capacity required for the battery. When the number of anode plates (or cathode plates) is greater than 100, the folding process is complicated. Therefore, the anode plate is used in the range of 1 to 100. It is better to use 1 to 50 anode plates, more preferably 2 to 20, and -11-(9) (9) 200401464 4 to 15 is the best. The details are as follows. As a cathode active material, lithium-transition metal oxide is optionally combined with a current conductive material, a binder, and additives such as an antioxidant and a flame retardant, dispersed in a suitable solvent, and then coated on a cathode current collector ( Such as aluminum sheet). The coated cathode current collector is dried, pressurized with a roller press, and then cut to an appropriate size to produce a cathode plate. Similarly, the anode active material and the binder are dispersed in an appropriate solvent, coated, dried, pressed, and cut to an appropriate size to produce an anode plate. As shown in Figs. 2a to 2c, the obtained cathode and anode plates were arranged in a predetermined order on one side of a separator coated with an ion conductive polymer material. The separators with electrode plates are continuously folded to produce a stack, in which each cathode plate and each anode plate are staggered with each other, and the taps of the cathode plate and the anode plate are individually overlapped so that the cathode plate and the anode plate are connected in parallel, and the staggered cathode Separated from the anode plate by a separator. After that, the stack is placed in a package, and an electrolyte solution is injected to disperse and feed between the cathode plate and the separator and between the anode plate and the separator. The steps of the method of the present invention are performed continuously to produce lithium secondary batteries on a large scale. For example, steps a) to d) can be performed continuously after the rolled separator is pressed out at an appropriate speed. In this way, since the electrode plate is adhered to only one side of the separator ', the adhesion procedure (step b) is simple and the yield is increased. In addition, the separator in which the electrode plates are arranged is folded in a fixed direction, rather than in a zigzag manner, so the folding process is simplified (step c). Meanwhile, the cutting of the end of the unrolled partition can be performed according to the operating conditions. That is, the cutting of one end of the unrolled partition may be between step a) and step b), between step b) and step c) (10) (10) 200401464 or between step C) and step d ). The taps of the cathode and anode plates are individually led to appropriate leads, such as aluminum and nickel leads, which are connected in parallel by ultrasonic welding. Then, the final battery is prepared by loading the stack into a package, injecting an electrolyte solution, and heat-sealing the package under vacuum. In this case, iron or aluminum is usually used as the packaging material. The invention is described more fully with reference to specific embodiments. However, it should be known that this example is for illustration only and should not limit the present invention. Many modifications may be made without departing from the scope and spirit of the invention. [Embodiment] Examples Example 1: Preparation of electrode plates Cathode plates are prepared by conventional methods: 1000 grams of Li Co 02 powder as a cathode active material, 5 grams of carbon black as a current conductive material, and 5 grams as The polyvinylidene fluoride of the binder was uniformly mixed, and then 100 ml of N-methylpyrrolidone was added to the mixture. The resulting solution was applied to both sides of an aluminum foil having a thickness of 15 m as a current collector, dried, and pressed with a roller press. The thickness of the cathode plate is 150 micrometers. Similarly, an anode plate was prepared: 100 g of stone black powder and 10 g of polyvinylidene fluoride as a binder were uniformly mixed, and then 100 ml of N-methylpyrrolidone was added to the mixture. The obtained solution was coated on both sides of a copper foil having a thickness of 15 m as an anode collector, dried, and pressed with a roller press. The thickness of the cathode plate is 150 micrometers. -13- (11) (11) 200401464 The cathode and anode plates are cut with a puncher to obtain cathodes and anodes as shown in Figure 1, where each cathode and anode plate has taps. The obtained cathode plate and anode plate are stored in a cassette. Example 2: Preparation of Battery (1) A polymer solution was prepared by mixing acetonitrile (purchased from Aldrich) and polyethylene oxide (purchased from Aldrich, average molecular weight 1,000, 000) at a weight ratio of 100: 3. . The obtained polymer solution was coated on one side of a porous polyethylene board (manufactured by TecklonTM, ENTEK, thickness: 25 micrometers), and the board was used as a separator for a liquid fixed transportation device, and had a thickness of 2 micrometers. Five cathode plates and six anode plates from the cassette are arranged in the order shown in FIG. 2 on the side of the device coated with the polymer solution, and then continuously folded along the fold line to form a stack shown in FIG. 3 . The protruding taps of the cathode and anode plates are led out by nickel and aluminum leads, and are individually welded in parallel using ultrasonic waves. The stack was placed in an aluminum laminate with a bag that could hold the stack, and mixed with 1.2 mol LiPF6 & 3 ml of ethylene carbonate and ethyl methyl carbonate (1: 1 volume) The electrolyte solution prepared by the solvent was injected into the bag. The bag was heat-sealed under vacuum to produce a lithium secondary battery with a thickness of 38 mm, a width of 35 mm, and a length of 62 mm. Example 3: Preparation of battery (2) A lithium secondary battery was prepared as described in Example], except that polymethyl methacrylate was used instead of polyethylene oxide. -14-(12) (12) 200401464 Comparative Example 1 The lithium secondary battery described in KR 3 09,6 04 was prepared according to the method described in Example 2. The different places were that five cathode plates were adhered to the separator in a predetermined order. One side coated with a polyethylene oxide solution. After that, the polyethylene oxide solution was coated on the other side of the separator, and five anode plates were adhered on the other side of the separator to obtain a separator in which the separator was sandwiched between the cathode plate and the anode plate. Configuration. Folding is performed in a zigzag manner to produce a battery. Test of battery cycle life The battery life of the battery of Example 2 was tested and compared with that of Example 1. The results are shown in FIG. 5. As shown in Fig. 5, the lithium secondary battery of the present invention retains a discharge capacity of 95% or more even after 40 cycles, while the battery of Comparative Example 1 has a discharge capacity of less than 90%. From these results, it was found that the battery of the present invention has far improved cycle life characteristics compared to Comparative Example 1. As described above, the method of the present invention does not require a lamination process to closely adhere the electrode film to the separator at high temperature and high pressure. In addition, it can easily provide batteries of various shapes without causing any damage to the electrode plates, as each electrode plate is used in a pre-cut form. Compared with the lithium secondary battery disclosed in KR 3 09,640, the method of the present invention can simplify the folding process and the adhesion process, because the electrode plate is only adhered to one side of the separator, and continuous folding is performed in a fixed direction instead of Performed in a zigzag manner. Therefore, the method of the present invention is suitable for continuous manufacturing of lithium secondary batteries, and can produce lithium secondary batteries at high yields and improved capacity. The produced lithium secondary battery has the advantages of each cathode plate and each (13) (13) 200401464 anode plate being stably separated by a separator held tightly in the battery to improve cycle life characteristics. [Schematic description] Figure 1 is a perspective view of an electrode plate with a tap, which is used to coat both surfaces of the current collector with a solution containing an electrode active material, and the coated current collector is cut to an appropriate Made of size. Figs. 2 to 2C are plan views showing a preferred configuration of the present invention of a plurality of electrode plates on one side of a separator. Fig. 3 is a sectional view of the stacked body obtained by continuously folding the configuration of Fig. 2a. FIG. 4 is a perspective view of the stack of FIG. 3. Fig. 5 is a characteristic diagram showing the cycle life of the battery of Example 2, compared with Comparative Example 1 'ο Component symbol comparison table 100 Electrode plate 10 1 Current pole set 102 Coating 103 Tap 20 20 Separator 202a-202e Cathode plate 2 03 a-2 03 f anode plate 204 folding line