200405604 玖、發明說明： (_ 一）發明所屬之枝術領域 本發明係關於一種組裝電化學電池的方法，以及其所製 成的電化學電池。 (_二）先前技術 具有鋰金屬陽極，以及中間可嵌入或插入鋰離子材料之 陰極的電池已爲人所知。如果是二次鋰電池或是可充電式 鋰電池’使用鋰金屬陽極是不符合要求的，因爲它會因爲 枝狀結晶而形成一些問題，但是，如果使用了一種如石墨 之類的嵌入材料，可使其製成的電池得到令人滿意的結果 。此種電池可被稱爲’’鋰離子’’電池，或者是”搖擺式”電池 ，因爲鋰離子會在充放電期間於兩種嵌入材料之間被交換。 此種電池可以使用一種鋰鹽在有機液體中所形成的溶液 做爲電解質，如碳酸丙烯酯，並且使用一種多孔的高分子 薄膜做爲隔離膜，如聚丙烯或聚乙烯，其與電解質溶液之 間不會進行交互作用。或者是，隔離膜也可以是一種如聚 偏二氟乙烯（或是含有偏二氟乙烯的共聚物）之多孔性高分 子薄膜’其可與電解質溶液進行交互作用而形成一種膠態 或固態的電解質。WO 0 1 /48 063敘述了一種製造微孔性高 分子薄膜的方法，該種高分子中至少主要係含有偏二氟乙 烯，並且此薄膜的厚度可以少於5 0微米。此種電解質薄膜 對於降低電池電阻方面是令人滿意的。但是，若薄膜厚度 約少於3 0微米時，當使用傳統的積層技術時，因爲需要施 以壓力和升溫，因此就很難將此電解質層積層於電極層上 -5- 200405604 ，又不會造成短路的危險。 (三）發明內容 依照本發明，提供了 一種製造鋰離子高分子電池的方法 ，該種電池含有至少一個陽極層和至少一個每一層皆含有 個別鋰離子插入材料的陰極層，以及至少一種多孔性高分 子薄膜將每一個陽極層和每一個陰極層隔開，其中每一個 陽極層和每一個陰極層皆摻入一種局分子黏結劑，此方法 包括將各別區域中排列整齊的點狀壓感性接著劑施用於每 一對相對表面其中的一個表面上；將陽極層、隔離膜和陰 極層予以組合，並且施以足夠的壓力，以使其發生黏著作 用；最後將一種電解質溶液注入組裝的電池中，以形成一 個電池。 這種壓感性接著劑可以是一種壓感性熱熔膠。値得一提 的是，接著劑必須不會溶解於電解質的溶劑中，也不會與 其它電池的電解質成份產生交互作用。它必須在電池的正 常溫度範圍內維持黏著性，雖然更好的情況是，它可在例 如1 1 0 °c的溫度下熔解，使得當它被過熱時，電池將會分 層。 各別區域可以是任何形狀，但是必須佔相對表面之面積 非常小的比例。它們可以是（例如）虛線狀，或者是以圓點 狀爲更佳。這些各別區域以不大於2.0 ni m 2爲較佳，又以不 大於1 · 0mm2爲更佳。它們之間較好是距離至少5 mm，但不 能大於1 00mm ’更佳的情況是距離介於8mm到！ 5mm之間 ，例如大約1 〇mm。它們可以形成一個方形的陣列，或者是 -6- 200405604 一個三角形的陣列。被接著劑所佔去隔離膜的面積只佔總 面積相當小的比例，所以接著劑不會對於電池的電氣性質 產生不利的影響。例如，接著劑佔去總面積的5 %或更少， 以2 %或更少爲佳，又以1 %或更少爲更佳，又以0.5 %或更 少爲更佳。不過，接著劑區域仍能確使電池組件維持積層 在一起，並且避免連續的組件彼此間滑動。 通常陽極層和陰極層爲扁平狀。在本發明特別佳的一個 實施例中，陽極層和陰極層爲扁平狀，並且接著劑佔隔離 膜總面積的5%或更少，以2%或更少爲佳，又以1%或更少 爲更佳，又以〇 . 5 %或更少爲更佳。 (四）實施方式 製作電極 藉由製成一種氧化鋰鈷鎳、小比例之導電性碳材和做爲 黏合劑之聚偏二氟乙烯（PVdF)均聚物（So Way grade 6 02 0)之 混合物的方式來製作陰極，這是在N -甲基吡咯烷酮（Ν Μ P ) 的溶液中鑄造’而Ν Μ P是做爲P V d F的溶劑之用。這種等 級之聚合物的特色在於具有相當低的熔流指數，在負荷爲 1 〇公斤及溫度爲2 3 0 °C的條件下，其數値小於〇 . 7克/1 0分 鐘。這種混合物係使用一種刮刀在鋁箔上進行鑄造，並且 通過一個溫度區間爲例如8 0 °C和1 2 0 t之間的乾燥機，以 確使NMP能蒸發出來。然後再重覆此步驟以生成一個雙面 的陰極。藉由後續的真空乾燥來進一步確使所有的NMP得 以被移除。 以經2 8 0 0 °C熱處理，具有少量石墨且粒徑大小爲6微米 200405604 的碳微粒和做爲黏著劑的PVdF 6 020均聚物之混合物來製 作陽極。這種混合物係依照類似於陰極製造方法中所述的 方法，在NMP中由溶液鑄造在銅箔上。 然後將數個具有凸出金屬箔標籤的矩形陽極片和陰極片 予以切割。在一個特定的實例中，陽極爲3 2毫米X 5 1毫米 ，而陰極則爲3 0毫米X 4 9毫米，每一個電極具有自一端凸 出9毫米寬的未塗佈矩形標籟。 電池組裝 參考第1圖，其所顯示的是電池在製造期間的側視圖， 然後將一個矩形的平板電池與微孔性均聚物PVdF所製成 厚度爲1 5微米且大小爲3 4毫米X 5 3毫米的矩形隔離片1 〇 (So Way等級602 0)組裝在一起，以隔開連續的陽極和陰極 。在這個實施例中，共有九個雙面的陰極片1 2和十個陽極 片14，其中有八個爲雙面，一個陽極片14a只在它的上表 面具有陽極混合物，而另一個陽極片1 4b則只在它的下表 面具有陽極混合物。 在一個陽極片1 4或陰極片1 2被堆疊之前，如第2圖所 示，它的頂面和底面皆點上一排排的熱熔膠2 0，其係由膠 槍（未於圖中顯示）所擠出的壓感性接著劑。每一個點20的 直徑爲1毫米，並且這些點在整個表面上形成一個矩形的 陣列，點與點之間的最近距離約爲9毫米。當每一個隔離 膜1 〇被置於電極堆之上時，它將被輕輕的壓下，以使得陽 極片1 4或其下方的陰極片1 2經由壓感性接著劑而與其上 方和下方的隔離膜1 〇黏著在一起。 -8- 200405604 然後將陽極標籤1 6與一個單鉛（未於圖中顯示）焊接在一 起，並且將陰極標籤1 8與一個單鉛（未於圖中顯示）焊接在 一起。 完成電池 然後將組裝的電池封入一個可撓曲的封裝材料中，並且 抽真空，以確使接著劑能確賓使組件牢牢的黏合在一起。 然後以3克的塑化液態電解質予以回塡，例如1莫耳的 Li PF6於碳酸乙烯酯/甲基碳酸乙酯混合物中所形成之電解 質。將此封裝的電池以膠帶密封。在貯存1 2小時以確保電 解質被所有電池的組件所吸收之後，將此可撓曲的封裝材 料予以焊接，以形成永久的密封。 在上述的實施例中，壓感性的接著劑爲BAM 9 72熱熔膠 壓感性接著劑（來自Bear do w和Adams有限公司），其係由 烴類樹脂（5 0-60重量°/〇)、礦油（20-3 0%)和熱塑性橡膠 (5-10%)之混合物所構成，這種熱塑性橡膠爲一種苯乙烯-異戊間二烯-苯乙烯嵌段聚合物。它是利用一種ITW Dynatec熱熔噴膠頭來施用，接著劑在受熱時具有夠低的黏 度，而可被擠出，以形成這些小圓點。當其冷卻時’接著 劑仍保有黏性，所以在組裝電池時不需要施壓來維持電極 片黏合在一起：單純的接觸即以足夠。雖然每一個陽極片 1 4或陰極片1 2上的這些點的圖案可以都一樣，但較好是 能在每一次都將圖案稍微移動一點，使得這些圓點連續的 陣列能彼此交錯；因此，能使得因爲這些圓點2 〇厚度所造 成電池厚度的增加降至最低。 -9- 200405604 所得的電池具有良好的電氣性質。 値得注意的是，有些電池雖與上述的這些電池略有不同 ，但仍屬於本發明之範疇。特別是這些組件的大小可以與 前面所述者不同。電極材料亦可與前面所述者不同，例如 陰極材料可以是例如LiCo02或LiNi〇2，或者是尖晶石 LiMn204等材料，或是以氧化釩爲基材。陽極片或陰極片 的數目可與前述者不同。並且，隔離膜10的厚度亦可不同 ，如20或30微米，並且可以是不同的材料，如PVdF或 是一種PVdF/六氟丙烯共聚物，或是聚乙烯（例如Tonen材 料）。 熱熔膠壓感性接著劑可以和前述之組成不同，雖然此種 接著劑通常是由一種增黏性樹脂、塑化油、安定劑和/或一 種抗氧化劑及一種苯乙烯-丁二烯-苯乙烯或者是一種苯乙 烯-異戊間二烯-苯乙烯之嵌段共聚物（其爲熱塑性橡膠）所 構成。這種共聚物也可以是乙烯-醋酸乙烯酯、醋酸烷基酯 或是一種以丙烯爲基的聚合物。値得注意的是：這種接著 劑必須不會和電池的其它成份進行化學反應，特別是和電 解質；它在沈積之後必須仍能維持黏性；並且它必須具有 流動特性，以使其能形成液滴，因此，它在適當的操作溫 度之下必須具有相當低的黏度。例如，接著劑在1 5 0 °C的 溫度下’較好是具有布魯克菲爾（Brookfield)黏度 (1 2 0 0厘泊）或更小，又以〇 . 8 p a · s ( 8 〇 〇厘泊）或更小爲較佳 ’尤以0 · 4 P a · s ( 4 0 0厘泊）或更小爲最佳。 本發明可以快速的組裝堆疊式的電池，而且這種組裝可 -10- 200405604 以被自動化。此外，這些電池的每一個電極可具有相當大 的表面積。也可以選擇一種在高溫條件（例如n )下會軟 化的接著劑，以提供額外的電池斷電性能。 L五）圖式簡單說明 現在要針對本發明做更進一步的敘述，只是用來舉例之 用，並且參考所附的圖，其中： 第1圖顯示了本發明電池在組裝時的側視圖；以及 第2圖顯示了第丨圖之電池中的陰極片的視圖，該圖係 由俞頭A所指之方向看去。 主ϋ分二之代表符號說明200405604 (1) Description of the invention: (_) Field of the invention to which the invention belongs The present invention relates to a method for assembling an electrochemical cell and the electrochemical cell produced by the method. (_II) Prior art Batteries having a lithium metal anode and a cathode in which a lithium ion material can be inserted or inserted are known. If it is a secondary lithium battery or a rechargeable lithium battery, the use of a lithium metal anode is not satisfactory because it will cause some problems due to dendritic crystals. However, if an embedded material such as graphite is used, The battery can be made to obtain satisfactory results. This type of battery can be referred to as a 'lithium-ion' battery, or a "swing" battery, because lithium ions are exchanged between the two intercalating materials during charge and discharge. This battery can use a solution of a lithium salt in an organic liquid as an electrolyte, such as propylene carbonate, and a porous polymer film as a separator, such as polypropylene or polyethylene. There is no interaction between them. Alternatively, the separator can also be a porous polymer film such as polyvinylidene fluoride (or a copolymer containing vinylidene fluoride), which can interact with the electrolyte solution to form a colloidal or solid Electrolyte. WO 0 1/48 063 describes a method for manufacturing a microporous high-molecular film. The polymer at least mainly contains vinylidene fluoride, and the thickness of the film can be less than 50 microns. Such an electrolyte film is satisfactory in reducing the resistance of a battery. However, if the thickness of the thin film is less than about 30 micrometers, it is difficult to laminate the electrolyte layer on the electrode layer because of the pressure and temperature increase when using the traditional multilayer technology. Risk of short circuit. (C) Summary of the Invention According to the present invention, a method for manufacturing a lithium ion polymer battery is provided. The battery includes at least one anode layer and at least one cathode layer each containing an individual lithium ion intercalating material, and at least one kind of porosity. A polymer film separates each anode layer from each cathode layer, and each anode layer and each cathode layer is doped with a local molecular adhesive. This method includes aligning the dot-shaped pressure sensitivity in each region. The adhesive is applied to one of each pair of opposing surfaces; the anode layer, the separator, and the cathode layer are combined and applied with sufficient pressure to cause them to adhere; finally, an electrolyte solution is injected into the assembled battery To form a battery. The pressure-sensitive adhesive may be a pressure-sensitive hot-melt adhesive. It is worth mentioning that the adhesive must not dissolve in the solvent of the electrolyte or interact with the electrolyte components of other batteries. It must maintain adhesion over the battery's normal temperature range, although better yet, it can melt at temperatures such as 110 ° C, so that when it is overheated, the battery will separate. The individual areas can be of any shape, but must occupy a very small proportion of the area of the opposing surface. They can be, for example, dotted lines or more preferably dots. These respective areas are preferably not more than 2.0 ni m 2, and more preferably not more than 1.0 mm 2. The distance between them is preferably at least 5 mm, but it cannot be greater than 100 mm. More preferably, the distance is between 8 mm to! 5mm, such as about 10mm. They can form a square array, or -6- 200405604 a triangular array. The area of the separation film occupied by the adhesive only accounts for a relatively small proportion of the total area, so the adhesive does not adversely affect the electrical properties of the battery. For example, the adhesive occupies 5% or less of the total area, preferably 2% or less, more preferably 1% or less, and even more preferably 0.5% or less. However, the adhesive area still ensures that the battery modules are kept laminated together, and prevents continuous modules from sliding against each other. The anode layer and the cathode layer are generally flat. In a particularly preferred embodiment of the present invention, the anode layer and the cathode layer are flat, and the adhesive agent accounts for 5% or less of the total area of the separation film, preferably 2% or less, and 1% or more. Less is more preferable, and 0.5% or less is more preferable. (IV) Embodiments The electrodes are fabricated by making a lithium cobalt oxide, a small proportion of conductive carbon material, and a polyvinylidene fluoride (PVdF) homopolymer (So Way grade 6 02 0) as a binder. The mixture was used to make the cathode, which was cast in a solution of N-methylpyrrolidone (NM P), and NM P was used as a solvent for PV d F. This grade of polymer is distinguished by a rather low melt flow index, which is less than 0.7 g / 10 minutes at a load of 10 kg and a temperature of 230 ° C. This mixture is cast on aluminum foil using a doctor blade and passed through a dryer with a temperature range between 80 ° C and 120 t to ensure that NMP can evaporate. This step is then repeated to create a double-sided cathode. Further vacuum drying was used to further ensure that all NMPs were removed. The anode was made of a mixture of carbon particles having a small amount of graphite and having a particle size of 6 microns 200405604 and a PVdF 6 020 homopolymer as a binder after heat treatment at 2800 ° C. This mixture was cast from solution on copper foil in NMP according to a method similar to that described in the cathode manufacturing method. Several rectangular anode and cathode sheets with protruding metal foil labels were then cut. In a specific example, the anode is 32 mm x 51 mm, while the cathode is 30 mm x 49 mm. Each electrode has an uncoated rectangular tab protruding 9 mm wide from one end. Refer to Figure 1 for battery assembly, which shows a side view of the battery during manufacturing. Then, a rectangular flat battery and microporous homopolymer PVdF are made into a thickness of 15 microns and a size of 3 4 mm X 5 3 A rectangular separator 10 mm (So Way rating 6020) is assembled together to separate the continuous anode and cathode. In this embodiment, there are nine double-sided cathode sheets 12 and ten anode sheets 14, of which eight are double-sided. One anode sheet 14a has an anode mixture only on its upper surface and the other anode sheet 1 4b has an anode mixture only on its lower surface. Before an anode sheet 14 or a cathode sheet 12 is stacked, as shown in FIG. 2, the top and bottom surfaces of the sheet are marked with rows of hot-melt adhesives 20, which are operated by a glue gun (not shown in the figure). (Shown in)) Extruded pressure-sensitive adhesive. Each dot 20 has a diameter of 1 mm, and the dots form a rectangular array over the entire surface, and the closest distance between the dots is about 9 mm. When each separator 10 is placed on the electrode stack, it will be gently pressed so that the anode sheet 14 or the cathode sheet 12 below it will pass through the pressure-sensitive adhesive to the top and bottom of it. The separator 10 is stuck together. -8- 200405604 Weld the anode label 16 to a single lead (not shown) and the cathode label 18 to a single lead (not shown). After completing the battery, the assembled battery is sealed in a flexible packaging material, and a vacuum is applied to ensure that the adhesive can firmly bond the components together. It is then reconstituted with 3 g of a plasticized liquid electrolyte, such as the electrolyte formed by 1 mol of Li PF6 in a vinyl carbonate / methyl ethyl carbonate mixture. Seal this packaged battery with tape. After storage for 12 hours to ensure that the electrolyte is absorbed by all battery components, this flexible packaging material is soldered to form a permanent seal. In the above examples, the pressure-sensitive adhesive is BAM 9 72 hot-melt adhesive pressure-sensitive adhesive (from Bear do w and Adams Co., Ltd.), which is made of hydrocarbon resin (50-60 weight ° / 〇) It consists of a mixture of mineral oil (20-30%) and thermoplastic rubber (5-10%). This thermoplastic rubber is a styrene-isoprene-styrene block polymer. It is applied using an ITW Dynatec hot-melt spray head. The adhesive has a low enough viscosity when heated and can be extruded to form these small dots. When it cools down, the adhesive remains tacky, so no pressure is needed to keep the pads together when the battery is assembled: simple contact is sufficient. Although the pattern of these dots on each anode sheet 14 or cathode sheet 12 may be the same, it is better to move the pattern a little bit each time so that the continuous array of dots can stagger each other; therefore, It can minimize the increase in battery thickness caused by the thickness of these dots. -9- 200405604 The resulting battery has good electrical properties. It should be noted that although some batteries are slightly different from the above-mentioned batteries, they still belong to the scope of the present invention. In particular, the size of these components can be different from those described previously. The electrode material can also be different from the one described above. For example, the cathode material can be materials such as LiCo02 or LiNi〇2, spinel LiMn204, or the base material is vanadium oxide. The number of anode plates or cathode plates may be different from the foregoing. In addition, the thickness of the isolation film 10 can be different, such as 20 or 30 microns, and can be different materials, such as PVdF or a PVdF / hexafluoropropylene copolymer, or polyethylene (such as Tonen material). Hot melt adhesive pressure sensitive adhesives can be different from the aforementioned composition, although such adhesives usually consist of a tackifying resin, plasticizing oil, stabilizer and / or an antioxidant and a styrene-butadiene-benzene Ethylene or a styrene-isoprene-styrene block copolymer (which is a thermoplastic rubber). This copolymer can also be ethylene vinyl acetate, alkyl acetate or a propylene-based polymer. It should be noted that this adhesive must not react chemically with other components of the battery, especially with the electrolyte; it must still maintain viscosity after deposition; and it must have flow characteristics so that it can form The droplet, therefore, must have a relatively low viscosity at the appropriate operating temperature. For example, the adhesive at a temperature of 150 ° C 'preferably has a Brookfield viscosity (1,200 centipoise) or less, and at 0.8 pa · s (800%) Poise) or less is preferred, especially 0 · 4 P a · s (400 centipoise) or less is most preferred. The invention can quickly assemble stacked batteries, and this assembly can be automated. In addition, each of these batteries can have a considerable surface area. It is also possible to choose an adhesive that will soften under high temperature conditions (such as n) to provide additional battery power-down performance. L5) Brief description of the drawings Now, the present invention will be further described, but for illustration purposes only, and referring to the attached drawings, wherein: FIG. 1 shows a side view of the battery of the present invention when assembled; Fig. 2 shows a view of the cathode sheet in the battery of Fig. 丨, which is viewed from the direction indicated by Yutou A. Explanation of the main symbol of the two points
10 隔離膜 12 陰極片 14 陽極片 16 陽極標籤 18 陰極標籤 20 圓點 -11-10 Isolation film 12 Cathode sheet 14 Anode sheet 16 Anode label 18 Cathode label 20 Dot -11-