540174 A7 B7 五 發明説明 發明範疇 本毛明係有關-種電化學電池及其製造方法，特別係 有關-種包括具有多孔聚合物膜之分隔膜以及分隔膜支持 件之電化學電池及其製造方法。 相關技藝 裡離子弘池經《用於攜帶性設備如蜂巢式電話。裡聚 合物二次電池變成習知鋰二次電池的替代品，且具有設計 上之文化!·生4勢，習知鐘二次電池具有電解液茂漏、爆炸 等缺點。又替代金屬罐封裝材料，使賴袋。此外比較使 用金屬罐封裝的材料，可改良重量及每單位容積之容量密 度，因而由於此等特色可製造輕薄短小的電池。 至於鐘水合物二次電池，貝爾通訊研究公司曾經提出 種方法，其中多孔聚合物膜係經由萃取含括於聚合物 增㈣1製造。又提示-種方法其中聚合物膜保有電解液 未萃取增塑劑。 美國專利第6,235,006號揭示經由分散_聚合物 電極，不含增塑劑，經由使用非溶劑形成間隙，以及於 溫I縮結果所得產品製造電池之方法。但根據前述專利 :揭示，由於隨著時間的經過’電極及聚合物膜以加熱壓 縮’可料致電極與聚合物膜分離，故㈣對電池 電解液。此外，由於未使用無機添又/貝 ^ ^ lL B 成微小短路而 “合物膜係經由將電極浸泡於非溶劑 備，故电極可能受雜質影響，連續製法 ， 用。 於1產時並不 : 以 有製 本紙張尺度^^_標準_^格（210X297公釐） 於 室 案540174 A7 B7 Fifth invention description The scope of the invention is related to an electrochemical cell and a method for manufacturing the same, and particularly to an electrochemical cell including a separator with a porous polymer film and a separator support, and a method for manufacturing the same . Related Techniques: Ion Hiroike "For portable devices such as cellular phones. The polymer secondary battery has become a substitute for the conventional lithium secondary battery, and it has a design culture! · 4 potential, the conventional secondary battery has disadvantages such as leakage of electrolyte and explosion. It also replaces the metal can packaging materials and makes the bag. In addition, comparing the use of metal can packaging materials can improve the weight and capacity density per unit volume. Therefore, due to these characteristics, light and thin batteries can be manufactured. As for the bell hydrate secondary battery, Bell Communications Research has proposed a method in which a porous polymer membrane is manufactured by extracting and including it in the polymer Zengfan1. It is also suggested that a method in which a polymer film retains an electrolyte without extracting a plasticizer. U.S. Patent No. 6,235,006 discloses a method of manufacturing a battery by dispersing a polymer electrode, containing no plasticizer, forming a gap by using a non-solvent, and shrinking the resulting product at a temperature of 1 ° C. However, according to the aforementioned patent, it is disclosed that the electrode and the polymer film can be separated from each other due to the 'electrode and polymer film being heated and compressed' over time. In addition, the inorganic compound is not used to form a short circuit and the compound film is immersed in a non-solvent preparation, so the electrode may be affected by impurities. The continuous production method is used. No: ^^ _ standard_ ^ format (210X297mm) in paper case
——.--------#裝--------- (請先閲讀背面之注意事項再填寫本頁) 、tr— :線丨 4 540174 A7 _____B7_ 五、發明説明（2 ) 美國專利第6,218,051號揭示一種技術，其中含增塑劑 之PVdF聚合物膜以及多孔分隔膜與陽極及陰極藉加熱壓 合。該專利案中，因用作為增塑劑之苯二甲酸二丁酯（DBP) 係於加熱壓縮後萃取，故難以完全去除增塑劑。如此由於 量產低故無法獲得良好生產力。 美國專利第 5,720,780、5,460,904、5,456,000 及 5,418,091號揭示電池製造技術，其中經由添加氧化矽粒子 及苯二甲酸二丁酯作為增塑劑於PVdF製備之聚合物膜被 加熱壓合至電極。隨後經由將電池浸潰於可溶解DBP之溶 劑然後由電池萃取DBP，形成浸潰以電解液之孔隙。此種 情況下，由於聚合物膜與電極壓縮，故電解液的浸潰以及 用於卒取過程之溶劑及增塑劑的完全去除困難。又因聚合 物膜的收縮，故不可靠。又因量產率低以及製造因子的常 規化困難，故不易實際應用於產業上。 前述技術的關鍵問題在於為了抑制增塑劑萃取過程， 聚合物的收縮，執行藉加熱壓合聚合物膜之電極之方法。 如此導致增塑劑萃取過程的增塑劑去除不完全。此外，浸 潰以電解液作為後處理過程，需要較長時間，如此又導致 均勻浸潰的困難，因此難以獲得電極與聚合物膜間的均一 界面。 於組合用於二次電池之一聚烯為主的多孔分隔膜及聚 a物％，熱壓溫度係依據無機添加劑含量改變，但通常係 於兩於120°C溫度進行熱壓。如此當使用以聚烯為主之多孔 分隔膜時，支持膜之物理性質改變。又因量產期間萃取增 本紙張尺度適用中國國表標準（Qjs) Α4規格（210X297公爱） ——一--------•裝：： (請先閲讀背面之注意事項再填寫本頁) >\^τ :線， 五、發明説明（3 ) 塑劑需要的時間長，萃取可信度不足，故量產生產力低， 且量產的控制因素困難。於未使用多孔分隔膜之例，因厚 度不均故出現嚴重短路問題。 美國專利第 5,853,916、5,716,42卜 5,834，135、5,681，357 及5,688,293號揭示一種製造聚合物電池之方法，其中無需 增塑劑萃取過程。根據前述專利案之揭示，聚合物材料分 散至具有良好機械強度之多孔分隔膜後，結果所得產品熱 壓合至電極。然後，電池浸泡於電解液，讓電池浸潰以電 解液。由於電極熱壓造成浸潰電解液需要時間長，故生產 力降低。 發明概述 為了解決前述先前技藝之問題，本發明之目的係提供 一種具有多孔分隔膜之電化學電池，其中多孔膜具有良好 機械強度、與電極之良好黏著性、良好吸收性、以及良好 電解質維持特性，因而電化學電池有高容量，良好週期壽 命特性。 本發明之另一目的係提供多種容易製造前述電化學電 池之方法。 為了達成前述目的，本發明提供一種電化學電池包含 -陽極、-陰極以及—分隔膜其係插置於陽極與陰極間。 分隔膜包括分隔膜支持體。聚合物膜形成於支持體上，聚 合物黏結劑_成於聚合物訂。支㈣包㈣聚偏/乙 烯為主之聚合物。 該方法包含 本發明之另一目的可經由一種方法達成， 容 540174 五、發明説明（4 ) 下列步驟··形成-聚合物膜，其包括以聚偏氟乙婦為主之 聚合物於分隔膜支持體上；經由塗覆聚合物黏結劑於聚合 物膜上形成聚合物黏結劑膜；以及於約室溫至8〇。〇範圍之 溫度熱壓陽極及陰極於聚合物黏結劑膜上。 圖式之簡要說明 前述本發明之目的及優點參照附圖說明較佳具體實施 例之進一步細節將變成更為彰顯，附著中： 第1圖為根據本發明之較佳具體實施例製造之分隔膜 剖面圖； 第2圖為根據本發明之另一較佳具體實施例製造之分 隔膜剖面圖； 第3圖為包括根據本發明之聚合物分隔膜之填塞型鋰 二次電池之示意剖面圖； 第4圖為包括根據本發明之分隔膜，呈堆疊單電池形式 之堆豐型鐘二次電池之示意剖面圖； 第5圖為線圖顯示於實例丨電池製造期間，於增塑劑萃 取後，聚合物膜之厚度縮小速率與最終聚合物膜間之關 係，以及根據膜厚度之聚合物含量變化； 第6圖為線圖，顯示當根據實例1製造電池時，依據增 塑劑萃取時間，電池以1(：速率充電及放電所得之放電 量； 第7圖為線圖顯示根據實例丨，鋰聚合物電池以〇2€速 率充電及放電期間電壓相對於時間之側繪； (請先閲讀背面之注意事項再填寫本頁)——.-------- # 装 --------- (Please read the precautions on the back before filling this page), tr—: line 丨 4 540174 A7 _____B7_ V. Description of the invention ( 2) U.S. Patent No. 6,218,051 discloses a technology in which a PVdF polymer film and a porous separator film containing a plasticizer and an anode and a cathode are laminated by heating and pressing. In this patent, it is difficult to completely remove the plasticizer because dibutyl phthalate (DBP) used as a plasticizer is extracted after heating and compression. Thus, due to the low mass production, good productivity cannot be obtained. U.S. Patent Nos. 5,720,780, 5,460,904, 5,456,000, and 5,418,091 disclose battery manufacturing techniques in which a polymer film prepared by adding silicon oxide particles and dibutyl phthalate as a plasticizer in PVdF is heated and pressed to an electrode. Subsequently, the battery is impregnated with a solvent capable of dissolving DBP and then the DBP is extracted from the battery to form pores impregnated with the electrolyte. In this case, since the polymer film and the electrode are compressed, it is difficult to impregnate the electrolyte and completely remove the solvent and plasticizer used in the stroke process. It is also unreliable due to the shrinkage of the polymer film. In addition, due to the low volume yield and the difficulty in normalizing the manufacturing factors, it is not easy to be practically applied to the industry. The key problem of the aforementioned technology is to perform the method of heating and pressing the electrode of the polymer film in order to suppress the shrinkage of the polymer during the plasticizer extraction process. This results in incomplete plasticizer removal during the plasticizer extraction process. In addition, the impregnation takes an electrolytic solution as a post-treatment process, which takes a long time, which in turn leads to the difficulty of uniform impregnation, so it is difficult to obtain a uniform interface between the electrode and the polymer film. In the combination of a polyolefin-based porous separator and a polymer, which are used in secondary batteries, the hot-pressing temperature is changed according to the content of the inorganic additive, but it is usually hot-pressed at a temperature of two to 120 ° C. Thus, when using a polyolefin-based porous separator, the physical properties of the support membrane change. Because of the increase in the size of the paper during the mass production, the Chinese paper standard (Qjs) Α4 specification (210X297 public love) is applicable. ——------------ Installation: (Please read the precautions on the back before filling (This page) > \ ^ τ: Line, V. Description of the invention (3) Plasticizer requires a long time, insufficient extraction reliability, so mass production productivity is low, and the control factors of mass production are difficult. In the case where a porous separator is not used, a serious short circuit problem occurs due to uneven thickness. U.S. Patent Nos. 5,853,916, 5,716,42 and 5,834,135, 5,681,357, and 5,688,293 disclose a method for manufacturing a polymer battery in which a plasticizer extraction process is not required. According to the disclosure of the aforementioned patent case, after the polymer material is dispersed into a porous separator having good mechanical strength, the resulting product is thermally compression-bonded to an electrode. Then, the battery is immersed in the electrolyte, and the battery is impregnated with the electrolyte. Since it takes a long time to impregnate the electrolyte due to electrode hot pressing, the productivity is reduced. SUMMARY OF THE INVENTION In order to solve the foregoing problems of the prior art, an object of the present invention is to provide an electrochemical cell having a porous separator film, wherein the porous film has good mechanical strength, good adhesion to electrodes, good absorption, and good electrolyte maintenance characteristics Therefore, electrochemical cells have high capacity and good cycle life characteristics. Another object of the present invention is to provide a plurality of methods for easily manufacturing the aforementioned electrochemical cell. In order to achieve the foregoing object, the present invention provides an electrochemical cell including an anode, a cathode, and a separator, which are interposed between the anode and the cathode. The separation membrane includes a separation membrane support. The polymer film is formed on the support, and the polymer binder is formed on the polymer. It is a branched polyvinylidene / ethylene-based polymer. The method includes another object of the present invention which can be achieved by a method, content 540174. V. Description of the invention (4) The following steps: forming a polymer film, which includes a polymer mainly composed of polyvinylidene fluoride in a separation film On a support; forming a polymer adhesive film on the polymer film by coating the polymer adhesive; and at about room temperature to 80. A temperature in the range of 0 was hot-pressed on the polymer adhesive film at the anode and the cathode. BRIEF DESCRIPTION OF THE DRAWINGS The foregoing objects and advantages of the present invention will be described with reference to the accompanying drawings. Further details of the preferred embodiment will become more prominent, and in the process of attachment: FIG. 1 is a separation film manufactured according to a preferred embodiment of the present invention. Sectional view; Figure 2 is a sectional view of a separator film manufactured according to another preferred embodiment of the present invention; Figure 3 is a schematic sectional view of a plug-type lithium secondary battery including a polymer separator film according to the present invention; Fig. 4 is a schematic cross-sectional view of a pile-type clock secondary battery in the form of a stacked single cell including a separator film according to the present invention; Fig. 5 is a line drawing showing an example during battery manufacturing, after the plasticizer extraction The relationship between the thickness reduction rate of the polymer film and the final polymer film, and the change in the polymer content according to the film thickness; Figure 6 is a line chart showing when the battery is manufactured according to Example 1, according to the plasticizer extraction time, The battery discharges at a rate of 1 (: the rate of charge and discharge; Figure 7 is a line graph showing that according to an example, the voltage of a lithium polymer battery during charge and discharge at a rate of 0 € relative to Between the painted side; (Please read the notes and then fill in the back of this page)
第8圖為線圖顯示根據實例丨，鋰聚合物電池以i () c速Fig. 8 is a line diagram showing that according to the example, the lithium polymer battery has an i () c speed
一 7 率充電及放電期卩卩 + " 充電及放電效率相對於週期之關係； 第9圖為線圖鬼- ’、， 頒露Μ實例丨，以h〇c速率充電及放 电鐘聚合物電池期間 功間與週期之關係； 第10圖為線圖，歸干奸1 .、、、員不根壤—員例4，以ι·〇 c速率充電及 放電鋰聚合物電池期p 妨ϋ〜曰与 4間，放邊^谷1與週期之關係；及 第U圖為線圖，顯示根祿fj5，則。c速率充電及 %鋰聚合物電池期間’放事量與週期之關係。 發明之詳細說明 、本發明提供-種電化學電池，包含一陽極；一陰極； 、+刀隔膜該分隔膜係插置於陽極與陰極間，該分隔 膜匕括77 ^膜支持體，一聚合物膜形成於支持體上，以 及—聚合物黏結劑卿成於聚合物膜上，該支持體包括以 聚偏氟乙烯為主的聚合物。 4寸別’聚合物膜厚度較好約為1至50微米，聚合物黏结 劑膜較好塗覆於聚合物膜表面上，讓聚合物黏結劑膜覆蓋 約1-80%聚合物膜表面。 取本發明提供一種方法，該方法包含下列步驟··形成-承口物膜’其包括以聚偏氟乙烯為主之聚合物於分隔膜支 持體上，I由塗覆聚合物黏結劑於聚合物膜上形成聚合物 黏結劑膜’ ·以及於約室溫至㈣範圍之溫度熱壓陽極及陰 極於聚合物黏結劑膜上。 聚合物膜可藉後述多種方法製備。 百'先，聚合物膜之製備方法係經由混合约1〇〇份重量比 以承偏貺乙烯為主之聚合物约〗〇〇_3,〇〇〇份重量比溶劑以 540174 A7 B7 五、發明説明（6 ) 及約100-1，000份重量比增塑劑製備聚合物溶液；塗覆聚合 物溶液於分隔膜支持體；由塗覆後之聚合物溶液氣化溶 劑；以及使用萃取溶液萃取增塑劑。 第二，聚合物膜之製備係經由混合約100份重量比以聚 偏氟乙烯為主之聚合物與約100-3,000份重量比溶劑製備 聚合物溶液，將該聚合物溶液塗覆於分隔膜支持體上；由 塗覆後之聚合物溶液氣化溶劑；以及使用非溶劑形成孔隙。 第三，聚合物膜之製備係經由混合約100份重量比以聚 偏氟乙烯為主之聚合物，約100-3,000份重量比溶劑，以及 約100-1,000份重量比增塑劑製備聚合物溶液；使用刮刀葉 片法塗覆聚合物溶液於分隔膜上形成一層；於約室溫至130 °c範圍之溫度，藉熱壓塗層以及支持體而附著塗層於支持 體；以及使用萃取溶液萃取增塑劑。 第四，聚合物膜之製備係經由混合約100份重量比以聚 偏氟乙烯為主之聚合物與約100-3,000份重量比溶劑；使用 刮刀葉片法塗覆聚合物溶液於分隔膜上形成一層；於約室 溫至130°c範圍之溫度，藉熱壓塗層及支持體而附著塗層於 支持體；以及經由使用非溶劑形成孔隙。 後文將參照附圖說明本發明之進一步細節。 塗覆以聚合物之分隔膜製備如後。 至於用於聚合物膜之聚合物材料，可使用PVdF均聚物 或共聚物。因均聚物之結晶度高，具有不良離子傳導性， 故使用具有六氟丙烷（HFP)單位，較佳HFP單位8-25%之共 聚物。以聚氟乙烯為主之聚合物具有良好機械性質以及於 9 (請先閲讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS) A4規格（210X297公釐） 540174 A7 B7 五、發明説明（7 ) 室溫之高度離子傳導性，因此高度推薦使用以聚氟乙烯為 主之聚合物。 聚合物溶液係經由溶解聚合物於適當溶劑製備。至於 較佳溶劑，值得一提者有丙酮、四氫呋喃、甲基乙基甲酮、 二甲基甲醯胺、二甲基乙醯胺、四甲基脲、二甲亞颯、磷 酸三乙酯、磷酸三甲酯、正甲基吡咯啶酮等。聚合物相對 於溶劑之混合比約為1:1 -30重量比。 至於增塑劑，可使用苯二曱酸二丁酯（DBP)、己二酸 二甲酯等。本發明中，是否添加增塑劑係依據分隔膜製造 方法決定。當添加時，聚合物相對於增塑劑之混合比約 1:1〜10重量比。 無機填充劑如二氧化矽、沸石、三氧化二鋁等可添加 至溶液。當添加無機填充劑時，聚合物相對於無機填充劑 之混合比約為1:0.5〜2重量比，無機填充劑大小較佳不大於 10微米。 所得聚合物溶液藉球混合或物理攪拌等混合於溶劑， 較好為丙酮經歷約3-24小時時間。此項混合可於室溫進 行，但溫度可略微升高至約40至60°C溫度用於均勻混合聚 合物溶液。無機添加劑及增塑劑可於攪拌期間添加至其中。 攪拌後之聚合物溶液塗覆至分隔膜之支持體上。 至於本發明者使用之分隔膜支持體，值得一提者為習 用非織聚乙烯、非織聚丙烯、梭織PTFE、聚酯非織物、溶 劑紡績嫘縈、再生纖維素纖維、玻璃纖維、馬尼拉麻、瓊 麻紙漿及牛皮紙漿等。可單獨使用或組合使用。 10 (請先閲讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS) A4規格（210X297公釐） 540174A 7-rate charge and discharge period 卩 卩 + " Relationship between charge and discharge efficiency vs. cycle; Figure 9 is a line graph ghost-',, shows the example of 丨, charge and discharge the polymer at the rate of 〇c The relationship between work and cycle during the battery period; Figure 10 is a line diagram, which refers to the rape 1. ,,, and members are not rooted-Example 4, the lithium polymer battery is charged and discharged at ι · 〇c rate. Between ~~ and 4, the relationship between the margin ^ valley 1 and the cycle; and the U-th graph is a line graph showing the root fj5, then. Relation between c rate charging and% lithium polymer battery's amount of charge and cycle. Detailed description of the invention, the present invention provides an electrochemical cell comprising an anode; a cathode; and a knife diaphragm. The separator film is inserted between the anode and the cathode. The separator film comprises a 77 ^ film support and a polymer. The film is formed on a support, and a polymer binder is formed on the polymer film, and the support includes a polymer mainly composed of polyvinylidene fluoride. The thickness of the 4 inch polymer film is preferably about 1 to 50 microns, and the polymer adhesive film is preferably coated on the surface of the polymer film so that the polymer adhesive film covers about 1-80% of the surface of the polymer film. The present invention provides a method, which comprises the following steps: forming a mouthpiece film, which includes a polymer mainly composed of polyvinylidene fluoride on a support of a separation film, and polymerizing by coating a polymer adhesive A polymer adhesive film is formed on the material film 'and the anode and cathode are hot-pressed on the polymer adhesive film at a temperature ranging from about room temperature to ㈣. The polymer film can be prepared by various methods described later. Hundreds, first, the polymer film is prepared by mixing about 1,000 parts by weight of a polymer mainly composed of vinylidene vinylidene polymer, and the solvent is 540174 A7 B7. Description of the invention (6) and about 100-1, 000 parts by weight plasticizer to prepare a polymer solution; coating the polymer solution on a support of a separation membrane; vaporizing a solvent from the coated polymer solution; and using an extraction solution Extraction of plasticizers. Second, the polymer film is prepared by mixing about 100 parts by weight of a polymer based on polyvinylidene fluoride and about 100-3,000 parts by weight of a solvent to prepare a polymer solution, and coating the polymer solution on a separation film. On the support; vaporizing the solvent from the polymer solution after coating; and using non-solvents to form pores. Third, the polymer film is prepared by mixing about 100 parts by weight of a polymer based on polyvinylidene fluoride, about 100-3,000 parts by weight of a solvent, and about 100-1,000 parts by weight of a plasticizer. Solution; applying a polymer solution on the separator using a doctor blade method to form a layer; attaching the coating to the support by a hot-press coating and a support at a temperature ranging from about room temperature to 130 ° c; and using an extraction solution Extraction of plasticizers. Fourth, the polymer film is prepared by mixing about 100 parts by weight of a polymer based on polyvinylidene fluoride and about 100-3,000 parts by weight of a solvent; using a doctor blade method to coat the polymer solution on the separation film A layer; at a temperature ranging from about room temperature to 130 ° C, the coating is adhered to the support by hot-pressing the coating and the support; and pores are formed by using a non-solvent. Further details of the present invention will be described later with reference to the drawings. The polymer-coated separator was prepared as follows. As the polymer material for the polymer film, a PVdF homopolymer or copolymer can be used. Homopolymers have high crystallinity and poor ion conductivity, so copolymers with hexafluoropropane (HFP) units, preferably 8-25% HFP units, are used. Polyfluoroethylene-based polymers have good mechanical properties and are based on 9 (please read the precautions on the back before filling out this page) This paper size applies to China National Standard (CNS) A4 (210X297 mm) 540174 A7 B7 5 7. Description of the invention (7) High ion conductivity at room temperature, so it is highly recommended to use polymers based on polyvinyl fluoride. The polymer solution is prepared by dissolving the polymer in a suitable solvent. As for the preferred solvent, it is worth mentioning acetone, tetrahydrofuran, methyl ethyl ketone, dimethylformamide, dimethylacetamide, tetramethylurea, dimethylmethane, triethyl phosphate, Trimethyl phosphate, n-methylpyrrolidone and the like. The mixing ratio of the polymer to the solvent is about 1: 1 to 30 by weight. As the plasticizer, dibutyl phthalate (DBP), dimethyl adipate, and the like can be used. In the present invention, whether or not to add a plasticizer is determined according to the method for producing a separator. When added, the mixing ratio of polymer to plasticizer is about 1: 1 to 10 weight ratio. Inorganic fillers such as silica, zeolite, alumina, etc. can be added to the solution. When an inorganic filler is added, the mixing ratio of the polymer to the inorganic filler is about 1: 0.5 to 2 by weight, and the size of the inorganic filler is preferably not more than 10 microns. The obtained polymer solution is mixed with a solvent by ball mixing or physical stirring, and the acetone is preferably subjected to a period of about 3 to 24 hours. This mixing can be performed at room temperature, but the temperature can be raised slightly to about 40 to 60 ° C for uniform mixing of the polymer solution. Inorganic additives and plasticizers can be added to it during stirring. The stirred polymer solution is applied to the support of the separation membrane. As for the separator support used by the present inventors, it is worth mentioning the conventional non-woven polyethylene, non-woven polypropylene, woven PTFE, polyester non-woven fabric, solvent spinning fabric, regenerated cellulose fiber, glass fiber, Manila Hemp, jojoba pulp and kraft pulp. Can be used alone or in combination. 10 (Please read the precautions on the back before filling out this page) This paper size is applicable to China National Standard (CNS) A4 (210X297 mm) 540174
發明説明 較好使用具有高離子傳導性及良好吸收性且可浸潰以 電解液之梭織分隔膜。一般使用之多孔膜具有少數間隙及 不良電解質吸收能力。但當使用梭織分隔膜時，電解質吸 收能力提升，於聚合物界面移轉離子面積比高，故可獲得 良好容量及使用週期喜合房主#卜士。 卩特〖生此外，因梭織分隔膜比習 知分隔膜價廉，故可降低製造成本。又梭織分隔膜表面粗 糙，當用於支持體時避免可聚合物膜收縮。前述支持體中， 即使非織聚乙烯及非織聚丙烯’非屬梭織分隔膜，仍然顯 示良好功能’因而可用於本發明。 供參考用以習知貝_柯（Belle⑽）方法為例，若於聚合 物熱壓合至電極後，聚合物與電極間的黏合性減低，則聚 合物收縮。因而電池不可靠。 有兩種塗覆聚合物膜於分隔膜之方法。至於第一 法，溶液係經由喷霧法、刮刀葉片法、網印法等直接塗 於分隔膜之支持體上。塗覆後之分隔膜經由氣化溶劑轉: 包括聚合物膜之分隔膜。如此製備之分隔膜中，當分隔 不含增塑劑時，經由使用非溶劑形成孔隙；以及當分隔 包括增塑劑時係經由使用萃取溶劑形成孔隙。 至於第二方法，使用前述聚合物溶液，經由刮刀葉 法於分隔膜支持體上形成-層，該支持體較好為聚酯薄 (例如岔勒薄膜，商品名）該薄膜上已經塗覆矽。此時， 合物塗覆至約1-50微米厚度，更好塗覆成不大於1〇微米厚 度。熱壓合聚合物膜於分隔膜支持體之方法係於約室溫至 130°C實施，所需時間係依據熱壓之壓力及溫度決定。例如 本紙張尺度適用中國國家標準（CNS) A4規格（210X297公釐） 方 覆 膜 片 膜 聚 --------•裝…： (請先閲讀背面之注意事項再填寫本頁) ·、=& :線丨 540174 五、發明說明（9 , 當使用輥於約100t；溫度熱壓時，以至少1〇米7分鐘速度較 為只用。較好壓縮比係占總厚度之約丨-乃％。 刖述多種方法中之任一種方法，若添加增塑劑用以提 门孔隙度，則聚合物塗覆於支持體後，萃取出增塑劑。為 了提回孔隙度，當未添加增塑劑時利用非溶劑特性。兩種 方法中，作為溶劑可使用己烷、戊烷、甲苯、甲醇、乙醇、 四氯化石厌、鄰二氯苯、三氯乙烯、水等。此時兩種情況下 於岭船τ留時間不超過5分鐘。如此解決習知貝爾柯方法之 若干量產問題。 根據本發明，因聚合物塗覆於全體表面上之厚度薄， 不超過^述50微米，容易快速完成增塑劑的萃取而形成孔 =、^头貝爾柯方法為例，聚合物膜形成至約5 0- 1 〇〇微 米厚度、，俾便防止短路，故增塑劑之完全萃取相當困難， 需要約為1日之長時間才能完全萃取增塑劑。由於萃取需要 、才門長故連績製法變不可能，但本發明可解決該項問 題且達成連續處理。 第1圖為根據本發明之第_方法，經由直接塗覆聚合物 溶液於分隔膜上製備得之分隔膜之剖面圖。當聚合物溶液 直接塗覆於分隔膜之支持體5上時，聚合物用黏度低故浸 /貝於刀隔膜内側。浸潰後之聚合物經由形成孔隙方法轉成 多孔聚合物分隔膜。 第圖為根據本發明之第二方法，經由壓合聚合物膜至 分隔膜上製備之聚合物分隔膜之剖面圖。若已經形成為薄 膜之來。物膜壓合至分隔膜之支持體5上，形成空白空間， 540174 五、發明説明（ι〇 此處未曾植入聚合物7,故其離子傳導性以及浸潰以電解液 之能力比聚合物塗覆於分隔膜支持體案例高。因此更佳方 法係經由壓合預成形聚合物膜至分隔膜上而形成聚合物分 隔膜。但本發明也適用直接塗覆聚合物至分隔膜之方法。 如此如前述製備之聚合物分隔膜可施用至鋰聚合物二 次電池、電容器、感應器等。使用聚合物分隔膜製造鐘聚 合物二次電池之方法如後。 為了附著根據前述方法製備之聚合物分隔膜至電極， 黏性聚合物黏結劑塗覆至聚合物分隔膜。聚合物黏結劑係 藉喷霧法、浸潰法、刮刀葉片法、網印法、喷墨印刷法等 部分塗覆。經由部分塗覆方法，獲得良好黏著性，電解液 容易植入聚合物分隔膜與電極間形成空白空間，因此可製 造具有高容量及良好週期壽命特性之電池。 聚合物黏結劑係以其上形成聚合物膜之分隔膜表面約 1-80%經覆蓋之方式塗覆。若多孔聚合物膜表面覆蓋面 >、於1 /〇貝成乎然法獲得電極與分隔膜間之均句黏著性 右多孔聚合物膜表面覆蓋面積大於80%，則電解質浸潰 電極及分隔㈣部變困難。更好聚合物黏結劑之塗覆面 係覆蓋多孔聚合物膜表面約3-30%。 下列材料可用於聚合物黏結劑材料而無例外。 例如至於本發明有用的聚合物黏結劑材料，可使用 聚丁二烯為主的聚合物包括聚丙烯腈_ 丁二烯 (NBR)、聚苯乙烯_丁二烯橡膠(sbr)、聚苯乙烯-丁二烯 苯乙婦橡膠（SBS)、丙稀腈-丁二婦-苯乙«膠(ABS)、聚 積 於 積 以 膠 本紙張尺舰财關緖準^7^^0X297公爱)DESCRIPTION OF THE INVENTION It is preferable to use a woven separator having high ion conductivity and good absorption and capable of being impregnated with an electrolytic solution. Generally used porous membranes have few gaps and poor electrolyte absorption capacity. However, when a woven separator is used, the electrolyte absorption capacity is improved, and the area ratio of the transferred ions at the polymer interface is high. Therefore, a good capacity and life cycle can be obtained. In addition, since the woven separator film is cheaper than the conventional separator film, the manufacturing cost can be reduced. In addition, the surface of the woven separator film is rough to avoid shrinkage of the polymerizable film when used in a support. Among the aforementioned supports, even if the non-woven polyethylene and the non-woven polypropylene 'are not woven separator films, they still show good functions' and can be used in the present invention. For reference, the Belle⑽ method is used as an example. If the polymer is thermocompression bonded to the electrode, the adhesion between the polymer and the electrode decreases, and the polymer shrinks. The battery is therefore unreliable. There are two methods of applying a polymer film to a separation film. As for the first method, the solution is directly applied to the support of the separation film via a spray method, a doctor blade method, a screen printing method, or the like. The coated separator is converted by a gasification solvent: a separator including a polymer film. In the thus-prepared separation film, when the separation does not contain a plasticizer, pores are formed by using a non-solvent; and when the separation includes a plasticizer, pores are formed by using an extraction solvent. As for the second method, the aforementioned polymer solution is used to form a layer on a separator support by a doctor blade method, and the support is preferably a thin polyester (for example, a Challe film, trade name) which has been coated with silicon. . At this time, the composition is coated to a thickness of about 1 to 50 microns, and more preferably to a thickness of not more than 10 microns. The method of heat-pressing a polymer film on a support for a separation film is performed at about room temperature to 130 ° C, and the time required is determined according to the pressure and temperature of the hot-pressing. For example, this paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm). Fang Laminated film Poly --------- • Installation: (Please read the precautions on the back before filling this page) · 、 = &Amp;: line 丨 540174 V. Description of the invention (9, when using a roller at about 100t; temperature hot pressing, it is only used at a speed of at least 10 meters and 7 minutes. The better compression ratio is about the total thickness 丨-%. Any one of the methods described above. If a plasticizer is added to improve the porosity of the door, the polymer is coated on the support and the plasticizer is extracted. In order to restore the porosity, when The plasticizer is added using non-solvent properties. In both methods, hexane, pentane, toluene, methanol, ethanol, tetrachloride, o-dichlorobenzene, trichloroethylene, water, etc. can be used as the solvent. At this time In both cases, the dwell time on the ridge boat is no more than 5 minutes. This solves some of the mass production problems of the conventional Belco method. According to the present invention, because the thickness of the polymer coating on the entire surface is thin, it does not exceed 50 Micron, it is easy to quickly complete the extraction of plasticizer to form pores =, scalp The Elko method is taken as an example. The polymer film is formed to a thickness of about 50-1000 microns, which prevents short circuits. Therefore, the complete extraction of the plasticizer is quite difficult. It takes about 1 day to fully extract the plasticization. Due to the need for extraction and long-term expertise, continuous production method becomes impossible, but the present invention can solve this problem and achieve continuous processing. Figure 1 shows the method _ according to the present invention, by directly coating the polymer solution on A cross-sectional view of the separation membrane prepared on the separator. When the polymer solution is directly coated on the support 5 of the separation membrane, the polymer has a low viscosity and is dipped / shelled on the inside of the knife diaphragm. The polymer after immersion passes through The method of forming pores is converted into a porous polymer separation film. The figure is a cross-sectional view of a polymer separation film prepared by laminating a polymer film onto the separation film according to the second method of the present invention. If it has been formed into a thin film. The material film is pressed onto the support 5 of the separation film to form a blank space. 540174 V. Description of the invention (The polymer 7 has not been implanted here, so its ion conductivity and the ability to impregnate with the electrolyte are higher than the polymer Painted The case of the separator support is high. Therefore, a better method is to form a polymer separator by laminating a pre-formed polymer film onto the separator. However, the present invention is also applicable to a method of directly coating a polymer to the separator. The polymer separator prepared as described above can be applied to lithium polymer secondary batteries, capacitors, inductors, etc. The method for manufacturing a clock polymer secondary battery using a polymer separator is as follows. In order to attach the polymer component prepared according to the foregoing method, Diaphragm to electrode, adhesive polymer adhesive is applied to the polymer separation film. Polymer adhesive is partially applied by spraying, dipping, doctor blade, screen printing, inkjet printing, etc. Part of the coating method achieves good adhesion, and the electrolyte is easily implanted into the polymer separation membrane and the electrode to form a blank space. Therefore, a battery with high capacity and good cycle life characteristics can be manufactured. The polymer binder is applied by covering about 1-80% of the surface of the separator film on which the polymer film is formed. If the surface coverage of the porous polymer membrane is greater than 80%, the average coverage of the surface of the porous polymer membrane is greater than 80% if the surface coverage of the porous polymer membrane is equal to 1/0. Ministry becomes difficult. The coating surface of the better polymer binder covers about 3-30% of the surface of the porous polymer film. The following materials can be used for polymer adhesive materials without exception. For example, as the polymer binder material useful in the present invention, polybutadiene-based polymers can be used, including polyacrylonitrile butadiene (NBR), polystyrene butadiene rubber (sbr), polystyrene -Butadiene Styrene (SBS), Acrylonitrile-Butadiene-Styrene «Glue (ABS), Accumulated on a Rubber Paper Ruler, Ship Caiguan Guanxun Zhuan ^ 7 ^^ 0X297 Public Love)
--------•裝…： (請先閲讀背面之注意事項再填寫本頁) -訂 :線丨 540174 A7 B7 五、發明説明（η ) 丁二烯等；合成或天然橡膠包括聚二甲基矽氧烷、聚異戊 間二烯、聚氯丁二烯、聚異丁烯、乙烯丙烯橡膠等；以丙 烯酸系為主之樹脂包括聚（丙烯酸烷酯）、聚（甲基丙烯酸烷 酯）、聚（乙基丙烯酸烷酯）、其共聚物及其組合；以聚醚為 主之聚合物包括聚環氧乙烷、聚氧亞甲基、聚環氧丙烷、 其共聚物及其組合；以氟為主之聚合物包括聚偏氟乙烯、 聚偏氟乙烯-六氟丙烷、聚氯三氟乙烯及其與乙烯之共聚 物、聚四氟乙烯、聚氟乙烯及其共聚物；以氯為主之聚合 物包括聚（氯乙烯）及聚（偏氯乙烯）等；聚合物包括苯環如聚 苯乙烯、酚樹脂等；聚合物包括OH基如聚乙烯醇、聚甲基 丙烯酸羥乙酯、乙烯-乙烯醇共聚物等；包括酸基之聚合物 如聚丙烯酸、聚苯乙烯磺酸、聚胺基酸等；可光硬化聚合 物如聚氰胺酸乙酯等；包括硝基之聚合物如聚丙烯腈、聚 甲基丙烯腈、其共聚物或混合物；聚烯類如聚乙烯、聚丙 烯等；聚乙烯基縮醛；聚乙烯基縮酮；聚乙烯基丁醛；聚 乙烯基曱醛；聚酯類；聚碳酸酯類；聚胺基甲酸酯類；聚 醯胺類；聚醯亞胺類等。 除了前述材料外，可使用其共聚物及混合物。更好使 用以橡膠為主之聚合物、以丙烯酸系為主之樹脂、以氟為 主之聚合物以及以氯為主之聚合物。 第3圖為根據前述方法製備之鋰聚合物二次電池之剖 面圖，其中具有優異浸潰性質以及良好維持性質之薄聚合 物分隔膜設置於分隔膜5支持體表面上，聚合物黏結劑6部 分塗覆於支持體上，因而提升與電極之黏著性。因使用具 14 (請先閲讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS) A4規格（210X297公釐） 540174 A7 B7 五、發明説明（l2 ) 有良好黏著性之聚合物，故無需高溫壓縮來附著電極。如 此聚合物之物理性質穩定。根據第3圖，至於陰極，係使用 其中陰極活性材料包括金屬鋰、鋰合金、合成石墨、天然 石墨、石油焦碳、攙雜焦碳等塗覆於銅電流集極1上之電 極。至於陽極，使用其中陽極主動材料包括有機硫化合物 如以鋰為主之LiCo02、LiNi02、LiCoNi02、LiMn204及硫 已經塗覆於铭電流集極上之電極。至於支持電極活性材料 用之電流集極，可使用格栅形式之網或箔形式。為何使用 箔形式之電流集極的原因在於電解液可絕佳浸潰於分隔膜 與電極間的空白空間，電解液極為容易浸潰於電池，因而 電解液經由電流集極造成浸潰特性的低劣不太顯著。此種 電解液之優異浸潰特性可改進生產力，因而容易以量產規 模製造具有均勻特性之電池。 至於用於製造鋰聚合物二次電池之電解液，可使用碳 酸伸乙酯（EC)、碳酸伸丙酯（PC)、石炭酸二乙酯（DEC)、竣酸 二甲酯（DMC)、碳酸乙酯甲酯（EMC)、τ - 丁内酯（τ -BL) 及其混合物。 鋰鹽例如過氯酸鋰（LiC104)、三氟甲烷磺酸酯 (LiCF3S03)、硼氟化鋰（LiBF4)、六氟磷酸鋰（LiPF6)、砷六 氟化鋰（LiAsF6)及其混合物可以約1.0M至2.0M之濃度使 用。此時若鋰鹽濃度低於1.0 M，則浸潰於聚合物電解質之 鋰含量不足，故電解液之鋰傳導性降低。又，若鋰鹽濃度 高於2M，則電解質黏度高，因電解質濃度差異造成的過電 壓變高。又顯示鋰聚合物於低溫性能問題。 15 (請先閲讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS) A4規格（210X297公釐） 540174 五、發明説明（I3 製造電池時，可製造填塞:毫备繞電池。多孔分隔 膜可施用於-般電池、二次電^^^。特別多孔分隔 膜可施用至電池其制咖〜及㈣:農料陽極於鐘二 人電池又可應用至使用具有琉或有機硫化合物之陽極之 電池。 最後本發明發展，容易經由分開聚合物分隔膜之兩種 能力而應用於量產。首先，塗覆於分隔膜支持體表面之以 聚偏敗乙烯為主之多孔隙聚合物可提高與電解液的親和 力，因而增加浸潰以電解液，且維持電解液於界面。又可 防止-般鋰聚合物二次電池之特徵性電解液洩漏問題， 解決短路造成的安定性問題。其次，因❹具有良好黏 性之聚合物黏結劑，故可達成電極與分隔膜間的良好黏， 性，非於高溫反而於約室溫至約8(rc即可達成，故聚合物 物理性質不變，可製造可靠的電池。又可製造-種電池， 其由於部分塗覆故經由分隔膜與電極間的空白空間，具有 浸潰以電解液之良好特性，以及具有電解液之良好維持特 性。 因黏著可於填塞型電池製造期間，藉黏著性聚合物 結劑，於聚合物之物理性質不變之溫度下重複實施多次 故可製造單電池型結構，而非製造成雙電池型結構，雙 池型結構乃習知貝爾柯方法之—大弱點。換言之，習知％ 池之製法係填塞具有陰極/分賴/陽極/分隔膜/陰極結構 之多數單元電極而製造雙電池。但於此種情況下，陰極與 陰極彼此接觸因而造成難以發揮電池的最理想性能。但本 黏 電 電 本紙張 尺度適用中_標準（⑽）A4^ (繼297公幻 16 可 著 著-------- • Install…: (Please read the precautions on the back before filling this page)-Order: Line 丨 540174 A7 B7 V. Description of the invention (η) Butadiene, etc .; synthetic or natural rubber includes Polydimethylsiloxane, polyisoprene, polychloroprene, polyisobutylene, ethylene propylene rubber, etc .; acrylic-based resins include poly (alkyl acrylate), poly (alkyl methacrylate) Esters), poly (alkyl acrylate), copolymers thereof, and combinations thereof; polyether-based polymers include polyethylene oxide, polyoxymethylene, polypropylene oxide, copolymers thereof, and Combination; fluorine-based polymers include polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropane, polychlorotrifluoroethylene and its copolymers with ethylene, polytetrafluoroethylene, polyfluoroethylene and its copolymers; Chlorine-based polymers include poly (vinyl chloride) and poly (vinylidene chloride); polymers include benzene rings such as polystyrene and phenol resins; polymers include OH groups such as polyvinyl alcohol and polymethacrylic acid Hydroxyethyl esters, ethylene-vinyl alcohol copolymers, etc .; polymers including acid groups such as polyacrylic acid, poly Styrene sulfonic acid, polyamino acid, etc .; light-curable polymers such as ethyl cyanurate, etc .; polymers including nitro such as polyacrylonitrile, polymethacrylonitrile, copolymers or mixtures thereof; polyene Such as polyethylene, polypropylene, etc .; polyvinyl acetals; polyvinyl ketals; polyvinyl butyral; polyvinyl amaldehyde; polyesters; polycarbonates; polyurethanes; poly Fluoramines; polyfluorene imines. In addition to the foregoing materials, copolymers and mixtures thereof can be used. It is better to use rubber-based polymers, acrylic-based resins, fluorine-based polymers, and chlorine-based polymers. FIG. 3 is a cross-sectional view of a lithium polymer secondary battery prepared according to the foregoing method, in which a thin polymer separation film having excellent impregnation properties and good maintenance properties is disposed on the surface of the support of the separation film 5 and a polymer binder 6 Partly coated on the support, thus improving the adhesion to the electrode. Due to the use of 14 (Please read the precautions on the back before filling in this page) This paper size applies to Chinese National Standard (CNS) A4 (210X297 mm) 540174 A7 B7 V. Description of the invention (l2) Polymerization with good adhesion Material, so no high temperature compression is needed to attach the electrode. As such, the physical properties of the polymer are stable. According to Fig. 3, as for the cathode, an electrode in which a cathode active material including metal lithium, lithium alloy, synthetic graphite, natural graphite, petroleum coke, doped coke, etc. is coated on a copper current collector 1 is used. As for the anode, electrodes in which the anode active material includes organic sulfur compounds such as lithium-based LiCo02, LiNi02, LiCoNi02, LiMn204, and sulfur have been coated on the current collector are used. As the current collector for supporting the electrode active material, a grid or a foil in the form of a grid can be used. The reason why the current collector in the form of a foil is used is that the electrolyte can be impregnated into the empty space between the separator and the electrode. The electrolyte is very easy to impregnate the battery. Therefore, the electrolyte impairs the impregnation characteristics through the current collector. Not too significant. The excellent impregnation characteristics of such an electrolyte can improve productivity, and thus it is easy to manufacture a battery with uniform characteristics at a mass production scale. As the electrolyte used in the manufacture of lithium polymer secondary batteries, ethylene carbonate (EC), propylene carbonate (PC), diethyl carboxylate (DEC), dimethyl carbonate (DMC), and carbonic acid can be used. Ethyl methyl ester (EMC), τ-butyrolactone (τ-BL) and mixtures thereof. Lithium salts such as lithium perchlorate (LiC104), trifluoromethanesulfonate (LiCF3S03), lithium borofluoride (LiBF4), lithium hexafluorophosphate (LiPF6), lithium arsenic hexafluoride (LiAsF6), and mixtures thereof may be about 1.0M to Use at a concentration of 2.0M. At this time, if the lithium salt concentration is less than 1.0 M, the lithium content impregnated in the polymer electrolyte is insufficient, so the lithium conductivity of the electrolytic solution is reduced. When the lithium salt concentration is higher than 2M, the electrolyte viscosity is high, and the overvoltage caused by the difference in electrolyte concentration becomes high. It also shows the problem of low temperature performance of lithium polymer. 15 (Please read the precautions on the back before filling this page) This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) 540174 V. Description of the invention (I3 When manufacturing a battery, you can manufacture stuffing: no spare winding battery .Porous separator can be applied to ordinary batteries and secondary electricity ^^^ Special porous separator can be applied to batteries and its production ~ and ㈣: agricultural anodes can be applied to the use of organic or organic batteries Sulfur compound anode battery. Finally, the present invention is developed and can be easily applied to mass production by separating the two capabilities of the polymer separation membrane. First, the porous poly-vinylidene-based polyporous coating is applied to the surface of the support of the separation membrane. Polymers can improve the affinity with the electrolyte, thus increasing the impregnation with the electrolyte, and maintaining the electrolyte at the interface. It can also prevent the characteristic electrolyte leakage problem of ordinary lithium polymer secondary batteries and solve the stability caused by short circuits. Secondly, because of the polymer adhesive with good adhesion, good adhesion between the electrode and the separator can be achieved, not at high temperature but at about room temperature to about 8 (rc can reach Therefore, the physical properties of the polymer are unchanged, and a reliable battery can be manufactured. Another kind of battery can be manufactured, which, due to partial coating, passes through the empty space between the separator and the electrode, has the good characteristics of being impregnated with an electrolyte, and The electrolyte maintains good characteristics. Because the adhesion can be repeated during the manufacture of the plug-in battery by the adhesive polymer binder at a temperature at which the physical properties of the polymer are unchanged, a single-cell structure can be produced instead of Manufactured into a dual-cell structure. The dual-cell structure is the weak point of the conventional Belco method. In other words, the conventional method of cell manufacturing is to fill most of the unit electrodes with a cathode / reliance / anode / separation membrane / cathode structure. Double battery. However, in this case, the cathode and the cathode are in contact with each other, which makes it difficult to exert the optimal performance of the battery. However, the paper is suitable for the standard of adhesive paper. Standard (⑽) A4 ^ (following 297 public magic 16 can be written)
--------#裝…： (請先閲讀背面之注意事項再填寫本頁) :線- 540174 A7 ________ 五、發明説明（14 ) 务明中，可％行於至溫至1 00。〇之重複加熱壓合，故可製造 具有陰極/分隔膜/陽極/分隔膜/陰極結構的單電池。 第4圖為包括本發明之分隔膜，呈填塞單電池形式之填 塞型鋰二次電池之示意剖面圖。根據第4圖，陰極包含銅電 流集極1及陰極主動材料2,陽極包含鋁電流集極3及陽極主 動材料4,陰極及陽極又藉具有良好黏著性之聚合物黏結劑 6黏著在一起。其中薄多孔聚合物膜形成於分隔膜支持體之 聚合物分隔膜係附著於陰極與陽極間。 本發明之較佳實例將說明其進一步細節如後。但須瞭 解本發明非僅限於下列實例。 〈實例1> PVdF共聚物（奇諾（Kynar) 2801 :商品名，依芙阿托肯 (Elf Atochem)公司製造），苯二甲酸二丁酯⑴Bp)及氧化石夕 以2:3:1重量比之比例添加至8〇重量％比丙酮溶劑，結果所 仔/谷液於60 C攪拌3小時。混合聚合物溶液移至密勒薄膜 (商品名’呈聚酯薄膜獲得）層上，於密勒薄膜層上已經藉 刮刀葉片法塗覆矽。此時所得層厚度為6_1〇微米。聚合物 層於100 C溫度以10米/分鐘速度壓合於作為支持體之梭織 分隔膜（TF4035 :商品名，日本小出公司製造）。此時，使 用有彈性橡膠附著其上之輥軸。製備完成之分隔膜聚合物 厚度為1-2微米。如此改善由習知聚合物電池製造方法所得 居度厚之問題。 製造後聚合物分隔膜浸沒於甲醇内經歷约1分鐘，俾去 除增塑劑，以10重量％溶解於丙酮之聚甲基丙烯酸丁酯藉 本紙張尺度適财11_標帛（CNSU·格⑵0X297公釐) _ ——17 --------- # 装…: (Please read the precautions on the back before filling out this page): Line-540174 A7 ________ V. Description of the invention (14) In the instructions, it can be performed at a temperature of up to 1% 00. 〇 repeated heating and pressing, so that can be produced with a cathode / separator / anode / separator / cathode structure. Fig. 4 is a schematic cross-sectional view of a stuffed lithium secondary battery in the form of a stuffed single cell including the separator of the present invention. According to Fig. 4, the cathode includes a copper current collector 1 and a cathode active material 2, the anode includes an aluminum current collector 3 and an anode active material 4, and the cathode and the anode are adhered together by a polymer adhesive 6 having good adhesion. A polymer separator film in which a thin porous polymer film is formed on a separator support is attached between a cathode and an anode. The preferred embodiments of the present invention will be described in further detail below. However, it should be understood that the present invention is not limited to the following examples. <Example 1> PVdF copolymer (Kynar 2801: trade name, manufactured by Elf Atochem), dibutyl phthalate ⑴Bp) and oxidized stone in a weight of 2: 3: 1 The ratio was added to 80% by weight of the solvent in acetone, and as a result, the seed / valley solution was stirred at 60 C for 3 hours. The mixed polymer solution was transferred onto a Miller film (obtained as a polyester film) layer, and silicon was coated on the Miller film layer by a doctor blade method. The thickness of the layer obtained at this time was 6-10 microns. The polymer layer was pressed at a temperature of 100 C at a speed of 10 m / min to a woven separator (TF4035: trade name, manufactured by Kode Co., Ltd.) as a support. At this time, a roller with elastic rubber attached thereto is used. The thickness of the prepared separation membrane polymer is 1-2 microns. In this way, the problem of a thick population obtained by the conventional method for manufacturing a polymer battery is improved. After manufacturing, the polymer separation film was immersed in methanol for about 1 minute, and the plasticizer was removed, and polybutyl methacrylate dissolved in 10% by weight in acetone. This paper was scaled to 11_standard (CNSU · 格 ⑵0X297) (Mm) _ ---- 17-
--------•裝…： (請先閱讀背面之注意事項再填寫本頁) 訂----- •線丨 540174 A7 B7 五、發明説明（l5 ) 喷霧方法分散於製備得之分隔膜。其上已經塗覆聚甲基丙 烯酸丁酯之分隔膜通過乾燥爐，去除丙酮。然後經由於80 °C加熱壓合分隔膜於陽極及陰極而完成填塞電池。藉加熱 壓合之電極於100-120°C溫度於真空放置約一日，因而去除 水含量及雜質。於低於120°C溫度下，分隔膜内部之聚合物 層物理性質不變。至於陽極使用LiCo02作為活性材料，至 於陰極使用MCMB作為活性材料。然後1M LiPF6於 EC/PC/DMC=2/1.2電解液添加至電池，如此所得電池置於 鋁積層包。然後執行密封處理。 〈實例2> 未使用氧化矽作為無機添加劑，共聚物（奇諾2801 :商 品名，依芙阿托肯製造）以及作為以聚偏氟乙烯為主之聚合 物之苯二甲酸二丁酯（DBP)以2/3重量比添加至80重量％丙 酮溶劑。結果所得產物於60°C攪拌3小時。混合聚合物溶液 轉變成一層，該層係於密勒薄膜（一種聚酯膜）上，密勒薄 膜上已經使用刮刀葉片法塗覆矽。此時，如此形成之聚合 物層厚度為6-10微米。聚合物層於140°C溫度及6米/分鐘速 度壓合至作為支持體之梭織分隔膜（TF4035 :商品名，曰本 小出公司製造）上。此時使用其上附著彈性橡膠之輥軸。製 備完成之分隔膜厚度太薄而其厚度為1-2微米。 製造後聚合物分隔膜浸潰於甲醇内約1分鐘，俾去除增 塑劑。聚丁二烯-苯乙烯橡膠分散於其中已經添加界面活性 劑之水。聚合物組成分濃度為8%重量比。橡膠溶液使用喷 膠喷霧於聚合物分隔膜表面上。經摩擦之塗膜通過乾燥烘 18 (請先閲讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS) A4規格（210X297公 540174 A7 _B7_ 五、發明説明（I6 ) 箱去除溶劑。結果所得產物於室溫壓縮而完成電極。於去 除殘水含量後，1M LiPF6於EC/PC/DMC二2/l/2電解液添加 至電池，如此所得電池置於鋁積層包。然後執行密封過程。 〈實例3> 奇諾741(商品名，依芙阿托肯公司製造）作為以聚偏氟 乙烯為主之聚合物以及氧化矽呈2/3重量比藉球混合於乾 燥態混合24小時。然後結果所得產物添加至80重量％丙酮 溶液隨後攪拌。此時增塑劑未添加至其中。混合聚合物直 接塗覆於作為支持體的梭織分隔膜（TF4035:商品名，曰本 小出公司製造）上。為了形成孔隙於已經通過乾燥爐俾去除 溶劑之聚合物分隔膜，將分隔膜浸泡於甲醇（甲醇為非溶劑) 經歷約1分鐘而形成孔隙。如此以實例1之相同方式，製造 妥之分隔膜組裝而完成電池。 <實例4> 實施實例1之相同程序，但使用非織聚烯膜作為分隔膜 支持體。此時，非織聚烯膜可施用於本發明，但其浸潰以 電解液以及維持電解液之特性比梭織分隔膜低劣。 〈實例5> 實施如實例1之相同程序，但使用梭織PTFE(高得斯 (Gore-Tex) PTFE分隔件：商品名，W.L. Gore公司製造）膜 作為分隔膜的支持體。此時發現PTFE之弱點之一的強度特 性可藉由塗覆聚合物層予以改良。 對所得電池之性能試驗進行如後。 第5圖顯示製造根據實例1之電池時，聚合物膜之厚度 19 (請先閲讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS) A4規格（210X297公釐） =低逮率與萃取增㈣後最終聚合物膜間之_，以及聚 &物含量隨厚度之變化。 #弟6圖顯示聚合物分隔膜根據實例1製造時，充電放電 於 > 週期可命特性與萃取增塑劑所需時關之關係。根 豕弟6圖’當萃取過程進行則分鐘時，幾乎可完全去除增 2 /現萃取可於5分鐘充分完成。當分隔膜厚度小於10 、’，可有利地進行增塑劑的萃取以及藉非溶劑形成孔 '、因增塑制的萃取過程係於壓縮至電極前實施，故可完 =去除=餘增塑劑。換言之，根據本發明，因聚合物厚度 厚，且溶劑處理過程係於電極與分隔膜塵合在—起前實 ^可縮短浸沒於萃取溶劑所料間。⑽量產率大增，（量 支持=先為其弱點）’可實施連續製法。又因分隔膜用作為 支持體，故可防止聚合物的收縮。 带裡^為根據本發明之實例卜於以g.2c速率充電及放 :鐘:“物電池期間電飾會相對於時間之作 二=二次電屋特性，其令充電係由怪電電流區及4:2 及區組成°當恆定㈣區縮小時，顯示較低電阻 :較4…7圖顯示低值定㈣區而具有絕佳性能的電 ㊉裡根據本發明之實例1，M.GC逮率充電及放 电經隶合物電池期間奋 充I及放電效率依週期 + 不根據本發明之實例】，以1.0C速率充電及於 電鋰聚合物電池期間放 放 間放”b力相對於週期作圖。鳩週期 540174 A7 B7 五、發明説明（18 ) 後發現週期壽命特性比最初容量高於9 0 %。 (請先閲讀背面之注意事項再填寫本頁) 第10圖顯示藉實例4製備之鋰聚合物電池以1C速率充 電及放電時之放電容量。比較第9圖，週期壽命特性略降。 但也可視為絕佳。 第11圖為根據本發明之實例5，於以1.0 C速率充電及 放電鋰聚合物電池期間放電容量相對於週期之作圖。 如前述，根據本發明，具有兩種性能之聚合物係分開 施用，故量產能力改善。製程之非均勻可藉由使用第一聚 合物組成物施用於本發明之聚合物層厚度變薄，以聚偏氟 乙烯為主之聚合物厚度變薄而減至最低。以聚偏氟乙烯為 主之聚合物層可改進電解液之浸潰，且改善與電解液之親 和力，故可提升電解液之浸潰特性及維持特性。又因萃取 過程並非於壓縮至電極後施行反而係於壓縮前施行，以及 聚合物層之厚度薄，故可完全免除增塑劑。又因增塑劑之 壓縮及萃取需要的時間短，故可快速進行製造過程。 因分隔膜用作為支持體，可防止增塑劑萃取期間聚合 物膜的收縮，可製造具有穩定物理性質之分隔膜。此外， 因可防止短路，故可製造適合用於製成之電池。又因聚合 物膜薄，容易去除增塑劑，故可製造具有穩定效能的聚合 物電池。 電池係使用其上完全或部分塗覆聚合物黏結劑的聚合 物分隔膜製造。因使用具有絕佳黏著性之聚合物黏結劑， 黏著甚至可於低溫施行而非於高溫施行，高溫將造成物理 性質改變。此外，因達成電極與聚合物分隔膜間之黏著為 本紙張尺度適用中國國家標準（CNS) A4規格（210X297公釐） 21 540174 A7 B7 五、發明説明（l9 ) 點黏著，電極與聚合物分隔膜間形成空白空間，故可製造 具有絕佳電解液浸潰特性及良好特性之電池。 雖然已經參照隨附之具體實施那本發明之細節， 但可未悖離本發明之精髓做出多項組成及相當 變化。 元件標號對照 1…銅電流集極 2…陰極活性材料 3…鋁電流集極 4…陽極活性材料 5…支持體 6…聚合物黏結劑 7…聚合物 (請先閲讀背面之注意事項再填寫本頁) r裝· 、可| :線丨 22 本紙張尺度適用中國國家標準（CNS) A4規格（210X297公釐）-------- • Install…: (Please read the precautions on the back before filling this page) Order ----- • Line 丨 540174 A7 B7 V. Description of the invention (l5) Spray method is used in preparation The obtained separation film. The separator on which the polybutyl methacrylate was coated was passed through a drying oven to remove acetone. Then, the battery was filled by pressing and pressing the separator on the anode and the cathode at 80 ° C. The electrode that was pressed by heating was placed under vacuum at 100-120 ° C for about one day, thereby removing water content and impurities. At temperatures below 120 ° C, the physical properties of the polymer layer inside the separator are unchanged. As for the anode, LiCo02 is used as the active material, and as the cathode, MCMB is used as the active material. Then 1M LiPF6 was added to the battery with an EC / PC / DMC = 2 / 1.2 electrolyte, and the battery thus obtained was placed in an aluminum laminate bag. Then, a sealing process is performed. <Example 2> Silica was not used as an inorganic additive, a copolymer (Kino 2801: trade name, manufactured by Evo Attoken), and dibutyl phthalate (DBP) as a polymer mainly composed of polyvinylidene fluoride. ) Is added to 80% by weight of acetone solvent in a 2/3 weight ratio. As a result, the obtained product was stirred at 60 ° C for 3 hours. The mixed polymer solution turns into a layer that is attached to a Miller film (a polyester film) that has been coated with silicon using a doctor blade method. At this time, the thickness of the polymer layer thus formed was 6-10 m. The polymer layer was pressed onto a woven separator film (TF4035: trade name, manufactured by Kodori Kode Co., Ltd.) as a support at a temperature of 140 ° C and a speed of 6 m / min. At this time, a roller with elastic rubber attached thereto was used. The thickness of the prepared separator was too thin and its thickness was 1-2 microns. After manufacturing, the polymer separator was immersed in methanol for about 1 minute, and the plasticizer was removed. The polybutadiene-styrene rubber is dispersed in water to which a surfactant has been added. The polymer composition concentration was 8% by weight. The rubber solution was sprayed onto the surface of the polymer separation film using a spray glue. The rubbed coating is dried and dried 18 (Please read the precautions on the back before filling this page) This paper size is applicable to Chinese National Standard (CNS) A4 specifications (210X297 male 540174 A7 _B7_ V. Explanation of the invention (I6)) Solvent removal As a result, the resulting product was compressed at room temperature to complete the electrode. After removing the residual water content, 1M LiPF6 was added to the battery in EC / PC / DMC 22 / l / 2 electrolyte, and the resulting battery was placed in an aluminum laminate package. Then executed Sealing process. <Example 3> Chino 741 (trade name, manufactured by Iv Atoken) as a polymer mainly composed of polyvinylidene fluoride and silicon oxide in a dry weight ratio of 2/3 by weight mixing with a ball 24 Hours. Then the resulting product was added to an 80% by weight acetone solution followed by stirring. At this time, a plasticizer was not added thereto. The mixed polymer was directly applied to a woven separator film as a support (TF4035: trade name, Yueben Xiao (Manufactured by the company). In order to form pores in the polymer separation membrane from which the solvent has been removed by a drying oven, the separation membrane is immersed in methanol (methanol is a non-solvent) for about 1 minute to form pores. In the same manner as in Example 1, a completed separator was assembled to complete the battery. ≪ Example 4 > The same procedure as in Example 1 was performed, but a non-woven polyolefin film was used as a separator support. At this time, the non-woven polyolefin film was used. It can be applied to the present invention, but its characteristics of impregnating electrolyte and maintaining electrolyte are inferior to woven separators. <Example 5> The same procedure as in Example 1 was performed, but using woven PTFE (Gore- Tex) PTFE separator: trade name, manufactured by WL Gore) membrane as a support for the separator. At this time, it was found that the strength characteristics of one of the weak points of PTFE can be improved by coating a polymer layer. Performance tests of the obtained batteries Proceed as follows. Figure 5 shows the thickness of the polymer film 19 when manufacturing the battery according to Example 1 (please read the precautions on the back before filling this page) This paper size applies to China National Standard (CNS) A4 (210X297) (Centi) = low capture rate and _ between the final polymer film after extraction enhancement, and the content of polymer & thickness as a function of thickness. # 6 Figure 6 shows that when the polymer separation film was manufactured according to Example 1, the charge and discharge were at> week The relationship between the life characteristics and the time required to extract the plasticizer. Figure 6 of the root figure 'When the extraction process is performed in minutes, it can be almost completely removed and the extraction can be fully completed in 5 minutes. When the thickness of the separation film is less than 10, ', the extraction of plasticizers and the formation of pores by non-solvents can be advantageously performed', because the extraction process of plasticization is performed before compression to the electrode, so it can be completed = removed = residual plasticizer. In other words, according to In the present invention, because the polymer is thick and the solvent treatment process is based on the combination of the electrode and the separation membrane, it can shorten the immersion in the space between the extraction solvent and the material. The yield is greatly increased. (Amount support = first is Its weak point) 'Continuous manufacturing method can be implemented. Since the separator is used as a support, shrinkage of the polymer can be prevented. The band ^ is an example according to the present invention. Charging and discharging at a rate of g.2c: Bell: "The electrical decoration during the battery will be two with respect to time = secondary electrical house characteristics, which makes the charging system from strange electric current. Zone and 4: 2 and zone composition ° When the constant chirped region is reduced, lower resistance is displayed: compared with 4 ... 7, the figure shows a low-value fixed chirped region with excellent performance. According to Example 1, M. The charge rate and discharge rate of the GC charge rate and discharge rate are determined by the cycle of the charge battery and the discharge efficiency according to the cycle + not according to the example of the present invention], charging at a rate of 1.0C, and discharging during the electric lithium polymer battery. Mapping to the cycle. Dove cycle 540174 A7 B7 V. Description of the invention (18) It was found that the cycle life characteristics were higher than 90% of the initial capacity. (Please read the precautions on the back before filling this page.) Figure 10 shows the discharge capacity when the lithium polymer battery prepared in Example 4 was charged and discharged at a rate of 1C. Comparing Fig. 9, the cycle life characteristics are slightly reduced. But it can also be considered excellent. Figure 11 is a plot of discharge capacity versus cycle during charging and discharging of a lithium polymer battery at a rate of 1.0 C according to Example 5 of the present invention. As described above, according to the present invention, polymers having two properties are applied separately, so the mass production ability is improved. The non-uniformity of the manufacturing process can be reduced by minimizing the thickness of the polymer layer applied to the present invention using the first polymer composition, and reducing the thickness of the polymer based on polyvinylidene fluoride. The polymer layer mainly composed of polyvinylidene fluoride can improve the impregnation of the electrolytic solution and improve the affinity with the electrolytic solution, so the impregnation and maintenance characteristics of the electrolytic solution can be improved. Because the extraction process is not performed after compression to the electrode, but is performed before compression, and the thickness of the polymer layer is thin, the plasticizer can be completely eliminated. Because the time required for compression and extraction of the plasticizer is short, the manufacturing process can be performed quickly. Since the separation film is used as a support, it is possible to prevent the shrinkage of the polymer film during the extraction of the plasticizer, and it is possible to manufacture a separation film having stable physical properties. In addition, since short-circuits can be prevented, a battery suitable for production can be manufactured. In addition, since the polymer film is thin and the plasticizer is easily removed, a polymer battery having stable performance can be manufactured. The battery is manufactured using a polymer separation film on which a polymer binder is completely or partially coated. Because of the use of polymer adhesives with excellent adhesion, adhesion can be performed even at low temperature instead of high temperature, and high temperature will cause changes in physical properties. In addition, due to the adhesion between the electrode and the polymer separation film, the Chinese national standard (CNS) A4 specification (210X297 mm) is applied to the paper size. 21 540174 A7 B7 V. Description of the invention (l9) Point adhesion, the electrode and polymer are separated. A blank space is formed between the separators, so a battery having excellent electrolyte impregnation characteristics and good characteristics can be manufactured. Although reference has been made to the details of the specific implementation of the present invention, many components and considerable changes can be made without departing from the spirit of the invention. Component number comparison 1 ... copper current collector 2 ... cathode active material 3 ... aluminum current collector 4 ... anode active material 5 ... support 6 ... polymer binder 7 ... polymer (please read the precautions on the back before filling in this (Page) r installed ·, can |: line 丨 22 This paper size applies to China National Standard (CNS) A4 specification (210X297 mm)