552733 五、發明說明（1 ) 本發明關係一種組合電化學電池之方法，層積電池零件 之方法，以及如此所製成之電化學電池。 I午多年來已知用錐金屬陽極’以及其中可被錐離子夾入 或插入之材料所成之陰極等製成電池。如此之電池可用鋰 鹽在如碳酸丙烯酯之有機液體中所成溶液作爲電解質；以 一種諸如濾紙或聚丙烯者作爲分離器。含有聚合物、助塑 劑、和鋰鹽之凝膠或固體電解質亦曾被建議使用而作爲電 解質。〇在第二或可再充電之鋰電池之情形中，使用鋰金屬 陽極者因枝蔓晶體之生長問題難以令人滿意，但是使用諸 如石墨之夾插材料已能製成令人滿意之電池^如此之電池 可稱之爲「鋰離子」電池，或「搖盪」電池，因爲鋰離子 是在充電與放電當中於兩種夾插材料之間互換2 凝膠或固體電解質可依Gozdz等人（美國專利5 296 3 1 8) 所述製成，用75至92%偏氟乙烯和8至25 %六氟丙烯之 共聚物作爲聚合物，其爲倂同鋰鹽和助塑之溶劑，如碳酸 伸乙酯/碳酸伸丙酯之混合物，被溶入於低沸點溶劑如四 氫呋喃者，並以溶液鑄造。如此之電解質，其只用熔融指 數極低之均聚物聚偏氟乙烯（PVd.F)者已載於GB 2 309 703 B (AEA Technology)。GB 2 309 701 B(AEA Technology)說 明如此之電解質組成物之黏著性如何可以用適當之單不飽 和基於聚合物鏈插枝而提高，在此狀況，聚合物鏈可能是 均聚物PVdF，或偏氟乙烯之共聚物。其亦可能先製成聚 合物材料之多孔膜，然後將膜浸入鋰鹽在有機溶劑中之溶 液內，使聚合物膜吸收電解質溶液而製成如此之固態聚合552733 V. Description of the invention (1) The present invention relates to a method for combining electrochemical cells, a method for stacking battery parts, and an electrochemical cell thus made. It has been known for many years to use a cone metal anode ' and a cathode formed of a material in which cone ions can be sandwiched or inserted, etc., to make a battery. Such a battery can use a solution of a lithium salt in an organic liquid such as propylene carbonate as the electrolyte; a separator such as a filter paper or polypropylene. Gels or solid electrolytes containing polymers, plasticizers, and lithium salts have also been proposed as electrolytes. 〇 In the case of a second or rechargeable lithium battery, the use of lithium metal anodes is difficult to satisfy due to the growth of branch crystals, but the use of intercalation materials such as graphite has been able to make satisfactory batteries ^ this is the case The battery can be called a "lithium ion" battery, or a "swing" battery, because lithium ions are interchanged between the two intercalation materials during charging and discharging. 2 Gel or solid electrolyte can be used according to Gozdz et al. (US Patent 5 296 3 1 8) It is made as described above, using a copolymer of 75 to 92% vinylidene fluoride and 8 to 25% hexafluoropropylene as a polymer, which is a different lithium salt and a plasticizing solvent, such as ethylene carbonate. The mixture of / propene carbonate is dissolved in a low boiling point solvent such as tetrahydrofuran and casted from a solution. Such an electrolyte, which uses only a homopolymer polyvinylidene fluoride (PVd.F) having an extremely low melt index, is already contained in GB 2 309 703 B (AEA Technology). GB 2 309 701 B (AEA Technology) shows how the adhesion of such an electrolyte composition can be improved with appropriate monounsaturation based on polymer chain cutting, in which case the polymer chain may be a homopolymer PVdF, or Copolymer of vinylidene fluoride. It is also possible to make a porous membrane of polymer material first, and then immerse the membrane in a solution of a lithium salt in an organic solvent to make the polymer membrane absorb the electrolyte solution to make such a solid state polymerization.
552733 五、發明說明（2) 物電解質，如 EP 0 730 3 1 6 A(Eef Atochem)所述。W0 0 1 /4 8 06 3 (AE A Technology)記述一種至少主要由偏氟乙烯 所構成之聚合物隔膜，且此種薄膜可以有小於50微米之 厚度。此種薄的電解質膜可如所希望減少電池電阻。然而 ，若用習知層積技術而須施加壓力並昇高溫度，以小於 30微米厚之薄膜則很難在無短路風險中將薄的電解質膜 層積於電極層上。 根據本發明，提供一種製造鋰離子聚合物電池之方法， (該電池含有一陽極層和一陰極層，各自含有鋰離子插入材 料，由多孔聚合物膜分隔，其中陽極層和陰極層各配有聚 合物膠合劑> 此方法包括組合陽極層、多孔聚合物隔膜、 和陰極層而形成一個電池總成，其中共聚物材料之薄的多 孔層被安置覆於陽極層和陰極層之面上。此方法也包括使 電池總成與一種液體接觸，該液體用於使共聚物材料溶劑 化（溶劑），但不使隔膜之聚合物材料溶劑化。然後從電池 總成將液體蒸發。最後將電解質溶液送入電池總成而成爲 電池 顯然隔膜之聚合物材料必須與各共聚物層不同，且可能 例如爲聚乙烯或聚丙烯，或均聚物PVdF(聚偏二氟乙烯） ，或其組成和溶解度均與各共聚物層不同之共聚物。多孔 性聚合物隔膜較佳爲厚度小於50微米之微孔膜，更佳爲 小於30微米，例如20微米。薄的共聚物層較佳爲小於 20微米厚’更佳小於1 〇微米厚，例如爲2微米厚。如此 極薄之層不易操作。其爲可以用積層法複於陽極和陰極上 552733 五、發明說明（3) ，或直接鑄成於陽極和陰極上，且在後一種情形中可以是 更薄（且在實際上也可以爲不均勻之厚度）其亦可以噴鍍於 陽極或陰極上，並且因而是間斷的。 液體可爲丙酮，其將局部溶合於薄的共聚物膜表面上， 因而黏著至膜上。此項溶劑化程序可以借助於保持電池總 成於如3(TC之稍高溫度（較佳不超過100°C )。隨後的蒸發 可進行於較高之溫度，例如60°C，較佳用減壓輔助。例 如電池總成可真空乾燥於60°C 3小時而確保所有的丙酮殘 痕被除去。代替丙酮，所用液體可爲丙酮與碳酸二甲酯之 混合物，其或可爲乙基-甲基-酮。此對在約6(TC之共聚物 爲有效之溶劑。 多孔的共聚物層和多孔的隔膜兩者較佳爲微孔性，其孔 較佳在0.1和10微米之間，更佳在0.5和2微米之間。如 WO 0 1/48 063所述，微孔膜可由溶劑/非溶劑混合物鑄造 ，或由潛在溶劑鑄造，所以整個程序可在無水或濕氣中進 行，減少在最後之薄膜或隔膜中有水存在之風險（其爲對 鋰離子電池之性質不利）。非溶劑應不但溶於溶劑，且應_ 與溶劑在實質上可以以任何比例混合。非溶劑之沸點較佳 高於溶劑者，較佳約爲高於20°C。例如，溶劑可以是二 甲基甲醯胺或二甲基乙醯胺，依此情形，適合之非溶劑爲 1-辛醇，其爲可溶於是項溶劑，且其沸點約爲194°C。 適用於偏二氟乙烯聚合物作爲溶劑和潛在溶劑之若干液 體列於表內。然而須知並非所有的溶劑可適用於所有各種 等級之聚合物。 552733 五、發明說明（4) 表1 溶劑 _沸點/°c 四氬呋喃 66 甲基乙基酮 80 二甲基甲醯胺 153 二甲基乙醯胺 166 二甲基亞楓 189 N-甲基吡咯烷酮 203 表2 潛在溶劑 溶解溫度/°c 沸點/°c 環己酮 70 157 4-羥-4-甲基-戊酮 100 160 5-甲基-2-己酮 102 144 1-甲氧基-2-丙醇 115 120 碳酸伸丙酯 80 240 酞酸二甲酯 1 10 260 在乾燥作用當中蒸發速率必須不爲快速，若爲快速乾燥 則會產生微孔，且亦可能導致形成不透之表皮而阻止其下 之液體蒸發。若用潛在溶劑，乾燥程序進行於低於用潛在 溶劑之溶解溫度之溫度。因此聚合物沉澱，相信因而生成 兩相：一富聚合物相，和一貧聚合物相。在潛在溶劑蒸發 時，富聚合物相之比例逐漸增加，而留下之貧聚合物相之 滴粒造就孔洞j形成。 本發明將另以實施例進一步說明，並參考附圖，其中： 552733 五、發明說明（5) 第1圖以曲線圖表示本發明電池在不同的放電率中電壓 對於充電之變化； 第2圖以曲線圖表示本發明另一電池之電壓對於充電之 變化； 第3圖表示被覆於電極上之共聚物薄膜照片；和 第4圖表示以噴鍍形成之變更共聚物薄膜照片。 製造多孔隔膜 將具有低熔融指數値（約爲0.7克/10分於10公斤和200°C ) 之均聚物PVdF(Solvay等級1015)在45°C之溫度於攪拌中 溶入於二甲基甲醯胺（DMF)，以15克PVdF溶於85克 DMF。然後逐滴少量加入9克之1-辛醇至聚合物溶液內， 在此次加入當中，小心混合，確使混合均勻。1 -辛醇之量 必須不致太大，否則溶液將成凝膠。然後混合此混合物於 另2小時之期間以確保均勻性。然後將所成三成分混合物 鑄造，用一醫師刮刀蓋於輥子上，在一鋁箔基質上形成一 層初始爲0.25毫米厚，然後轉經一 7米長之乾燥坑道分 別爲65°C和l〇〇°C溫度之連續乾燥區。其爲以0.5米/分通 過乾燥坑道。在各乾燥區內薄膜曝於1 4米/秒速度之熱空 氣流，除去蒸發之溶劑和非溶劑。乾燥空氣是獲自使空氣 通過一除濕機，使其露點爲-40°C。 在薄膜通過乾燥坑道之過程當中花了 1 4分鐘，溶劑和 非溶劑兩者逐漸蒸發（雖然兩者相遠低於其沸點），溶劑傾 向蒸發得較快。於是得到厚度約20微米之白色聚合物膜 ，用掃描電子顯微鏡分析表現其爲微孔狀。孔洞大小在 552733 五、發明說明（6) 0·5-2.0微米範圍內，通常直徑約爲1微米，至少在表面 上。已發現隔膜具有約53%之多孔性。 製成薄的共聚物層 以相似之方法製成薄的物層，溶解12克共聚物溶於88 克DMF中製成12重量％之PVdF/6HFP(偏二氟乙烯和6重 量％六氟丙烯）共聚物溶液。然後逐滴加入少量之1 -辛醇 至共聚物溶液，並在加入當中小心混合以使混合物均勻， 然後保持攪拌2小時。然後將所得三成分混合物鑄造，用 一醫師刮刀於一輥輪上，於鋁箔基質上形成一層，初始厚 度爲〇·〇6微米，然後確實乾燥如上述。 以此形成厚度約2微米之微孔層，孔洞與上述隔膜者相 似。 製成電極 陰極製自用尖晶石LiMn204、小比例之導電碳和用作膠 合劑之PVdF1015(如上述）均聚物所成之混合物，以在用 於PVdF之溶劑N-甲基吡咯烷酮（NMP)中之溶液鑄造。此 混合物是用醫師刮刀在一鋁箔上鑄成，並通過乾燥器，其 溫度區域例如爲80°C和120°C以保NMP之蒸發。然後此 程序被重複而產生雙面之陰極。於隨後再以真空乾燥確使 NMP全被除去。 一陽極製自由粒度爲10微米並熱處理於2800°C之消旋 碳微珠（MCMB 1 028)與小量石墨，和作爲膠合劑之PVdF 1 0 1 5等所成之混合物。此混合物於NMP中成爲溶液而鑄 於銅箔上，與在陰極中所述之形態相似。552733 V. Description of the invention (2) A physical electrolyte, as described in EP 0 730 3 1 6 A (Eef Atochem). W0 0 1/4 8 06 3 (AE A Technology) describes a polymer membrane composed of at least mainly vinylidene fluoride, and such a film may have a thickness of less than 50 microns. Such a thin electrolyte membrane can reduce battery resistance as desired. However, if the conventional lamination technique is used to apply pressure and raise the temperature, it is difficult to laminate a thin electrolyte membrane on the electrode layer without the risk of a short circuit with a thin film less than 30 microns thick. According to the present invention, a method for manufacturing a lithium ion polymer battery is provided. (The battery includes an anode layer and a cathode layer, each of which contains a lithium ion intercalating material, and is separated by a porous polymer film, wherein the anode layer and the cathode layer are each provided with Polymer Adhesive> This method includes combining an anode layer, a porous polymer separator, and a cathode layer to form a battery assembly, in which a thin porous layer of a copolymer material is disposed to cover the anode layer and the cathode layer. This method also includes contacting the battery assembly with a liquid that is used to solvate (solvent) the copolymer material, but does not solvate the polymer material of the separator. The liquid is then evaporated from the battery assembly. Finally, the electrolyte is evaporated The solution is fed into the battery assembly to become the battery. The apparent polymer material must be different from each copolymer layer, and may be, for example, polyethylene or polypropylene, or a homopolymer PVdF (polyvinylidene fluoride), or its composition and Copolymers with different solubility from each copolymer layer. The porous polymer membrane is preferably a microporous membrane with a thickness of less than 50 microns, and more preferably less than 30 microns. For example, 20 microns. A thin copolymer layer is preferably less than 20 microns thick, more preferably less than 10 microns thick, such as 2 microns thick. Such an extremely thin layer is not easy to handle. It can be laminated to the anode and 552733 on the cathode 5. Description of the invention (3), or cast directly on the anode and cathode, and in the latter case can be thinner (and can also be non-uniform thickness in practice) It can also be sprayed on On the anode or cathode, and is therefore intermittent. The liquid may be acetone, which will locally dissolve on the surface of the thin copolymer film and thus adhere to the film. This solvation procedure can be done by keeping the battery assembly in place such as 3 (Slightly higher temperature of TC (preferably not more than 100 ° C). Subsequent evaporation can be carried out at a higher temperature, such as 60 ° C, preferably assisted by reduced pressure. For example, the battery assembly can be vacuum dried at 60 ° C for 3 hours to ensure that all acetone residues are removed. Instead of acetone, the liquid used may be a mixture of acetone and dimethyl carbonate, or it may be ethyl-methyl-ketone. This pair is copolymerized at about 6 ° C Is an effective solvent. Porous copolymer layer Both porous membranes are preferably microporous, and their pores are preferably between 0.1 and 10 microns, more preferably between 0.5 and 2 microns. As described in WO 0 1/48 063, the microporous membrane can be Casting of non-solvent mixtures, or casting of latent solvents, so the whole process can be performed in anhydrous or moisture, reducing the risk of water in the final film or separator (which is detrimental to the properties of lithium-ion batteries). Non-solvent It should not only be soluble in the solvent, but should also be mixed with the solvent in virtually any ratio. The boiling point of the non-solvent is preferably higher than that of the solvent, more preferably about 20 ° C. For example, the solvent may be dimethylformamide Ammonium amine or dimethylacetamide, in this case, a suitable non-solvent is 1-octanol, which is soluble in this solvent and has a boiling point of about 194 ° C. Suitable for vinylidene fluoride polymers as Certain liquids of solvents and potential solvents are listed in the table. It should be noted, however, that not all solvents are suitable for all polymers of all grades. 552733 V. Description of the invention (4) Table 1 Solvent_boiling point / ° C tetrahydrofuran 66 methyl ethyl ketone 80 dimethyl formamide 153 dimethyl acetamide 166 dimethyl methylene amine N-methyl Pyrrolidone 203 Table 2 Latent solvent dissolution temperature / ° c Boiling point / ° c cyclohexanone 70 157 4-hydroxy-4-methyl-pentanone 100 160 5-methyl-2-hexanone 102 144 1-methoxy- 2-propanol 115 120 propylene carbonate 80 240 dimethyl phthalate 1 10 260 The evaporation rate during drying must not be fast. If it is fast drying, it will produce micropores, and it may also lead to the formation of impervious skin And prevent the liquid below it from evaporating. If a latent solvent is used, the drying process is performed at a temperature below the dissolution temperature of the latent solvent. As a result, the polymer precipitates and it is believed that two phases are formed: a polymer-rich phase, and a polymer-lean phase. As the potential solvent evaporates, the proportion of the polymer-rich phase gradually increases, while the remaining particles of the polymer-lean phase cause the formation of pores j. The present invention will be further described in embodiments with reference to the accompanying drawings, in which: 552733 V. Description of the invention (5) Figure 1 shows the change in voltage of the battery of the present invention with respect to charging at different discharge rates according to the graph; Figure 2 The graph shows the change in voltage of another battery of the present invention with respect to charging; FIG. 3 shows a photograph of a copolymer film coated on an electrode; and FIG. 4 shows a photograph of a modified copolymer film formed by spraying. To make a porous membrane, a homopolymer PVdF (Solvay grade 1015) with a low melt index 値 (about 0.7 g / 10 minutes at 10 kg and 200 ° C) was dissolved in dimethyl with stirring at a temperature of 45 ° C. Formamidine (DMF) was dissolved in 85 g of DMF with 15 g of PVdF. Then add 9 grams of 1-octanol to the polymer solution in small drops. During this addition, carefully mix to ensure that the mixture is uniform. The amount of 1-octanol must not be too large, otherwise the solution will gel. This mixture was then mixed for another 2 hours to ensure homogeneity. The resulting three-component mixture was then cast, covered with a doctor's spatula on a roller to form an initial layer of 0.25 mm thick on an aluminum foil substrate, and then passed through a 7-meter-long drying tunnel at 65 ° C and 100 °, respectively. Continuous drying zone at C temperature. It passed through the drying tunnel at 0.5 m / min. In each drying zone, the film was exposed to a hot air current at a speed of 14 m / s to remove evaporated solvents and non-solvents. Dry air was obtained by passing the air through a dehumidifier to a dew point of -40 ° C. It took 14 minutes for the thin film to pass through the drying tunnel. Both the solvent and the non-solvent gradually evaporated (although the two phases were far below their boiling points), and the solvent was inclined to evaporate faster. Thus, a white polymer film having a thickness of about 20 microns was obtained and analyzed by a scanning electron microscope to show that it was microporous. The pore size is in the range of 552733 V. Description of the invention (6) 0.5-2.0 micrometers, usually about 1 micrometer in diameter, at least on the surface. The separator has been found to have a porosity of about 53%. Make a thin copolymer layer. Make a thin layer in a similar way. Dissolve 12 grams of copolymer in 88 grams of DMF to make 12% by weight of PVdF / 6HFP (vinylidene fluoride and 6% by weight of hexafluoropropylene). ) Copolymer solution. A small amount of 1-octanol was then added dropwise to the copolymer solution and carefully mixed during the addition to make the mixture homogeneous, and then kept stirring for 2 hours. Then, the obtained three-component mixture was cast, and a doctor blade was used on a roller to form a layer on the aluminum foil substrate with an initial thickness of 0.06 m, and then it was dried as described above. Thus, a microporous layer having a thickness of about 2 micrometers was formed, and the pores were similar to those of the above-mentioned separator. Electrode cathode made from a mixture of spinel LiMn204, a small proportion of conductive carbon, and a homopolymer of PVdF1015 (as described above) used as a binder, in a solvent for PVdF N-methylpyrrolidone (NMP) Cast in solution. This mixture is cast on an aluminum foil with a doctor's spatula and passed through a dryer in a temperature range of, for example, 80 ° C and 120 ° C to keep the NMP from evaporating. This process is then repeated to produce a double-sided cathode. The NMP was subsequently removed by vacuum drying. An anode made of racemic carbon microbeads (MCMB 1 028) with a free particle size of 10 microns and heat treated at 2800 ° C, a small amount of graphite, and PVdF 1 0 1 5 as a binder. This mixture became a solution in NMP and was cast on copper foil, similar to the morphology described in the cathode.
552733 五、發明說明（7) 電池總成 陰極被夾於兩共聚物薄層之間’使各面完全被覆蓋’各 組件被置於離型紙之間使在壓機內產生20牛頓壓力之輥 輪間壓製於120 °C之溫度。使各零件因而層積於一起。 陽極也夾於共聚物薄層之間，並以相同之方式層積。 電池總成是以厚度2 0微米之多孔隔膜纒繞而分隔陽極 與陰極。各個如此之電池總成被包封於鋁/塑膠層積物所 成之密封封套內，並以小量之丙酮以〇·5克噴入於封套。 然後使容納有電池總成之封套保持30°C之溫度至少經5 分鐘期間。此升高之溫度以丙酮加強共聚物層表面之溶劑 化（溶劑）。 冷卻至大氣溫度後，電池總成從封套取出，然後真空乾 燥於60°C 3小時確使所有的丙酮殘被除去。 然後以塑化之液體電解質真空充入電池總成，例如用1 莫耳濃度之LiPF6於碳酸伸乙酯/碳酸乙酯甲酯之混合物中 。貯存1 6小時確使電解質已被所有的電池零件吸收，然 後真空包裝於撓性之包裝材料內。 其爲已被發現陽極與陰極兩者積層合於多孔隔膜，顯然 因爲在3 (TC被丙酮局部溶合使各共聚物層充份膠黏而接 著於多孔隔膜。因爲層積作用發生於無外壓施加之下因而 多孔隔膜無穿破之虞。令人驚奇者，局部溶合並不影響各 共聚物層之孔度，而且整個程序也不影響隔膜之孔度，所 以在加入助塑液體電解質之後電池具有良好的電氣性質。 例如，參考第1圖，其所表示爲對本發明電池雷壓與電 552733 五、發明說明（8) 容量，對於各種不同的放電率之變化，電池被充電和放電 於2.75伏與4.25伏之間。額定之電池電容量是在放電電 流（安培）之電容量，其數字等於電池電容量（安培小時）之 五分之一；此項放電被認爲是在C / 5之比率時之放電。額 定之電池電容量是決定於首先的五次放電和再充電之循環 ，其爲進行於C/5比率之一種估計。然後獲得第1圖所示 之量測。其將可見此特別電池之放電電容量約爲0.62安 培小時；電容量在放電率加大時稍減，但是甚至在放電率 爲2 C時可得之電容量約爲0 · 5 2安培小時，其爲額定電容 量之約8 4 %。 變更之電池 雖然在陰極內之活性插入物質在此情形中爲Li Co 02(獲 自FMC公司），陽極和陰極製自與上述者相同之方法。如 前，兩電極爲雙面。然後各電極被夾於兩片薄的微孔性共 聚物層之間（如上所述），並在各輥輪之間層積於升高之溫 度，如在前之實施例。 然後電池總成被燒以微孔性聚乙烯膜，厚度1 6微米， 分隔陽極與陰極，此種隔膜是由Τ ο n e n C h e m i c a 1 C 〇 r p供 給。各個如此之電池總成被裝入密封之封套內，並以少量 如0.5克之丙酮噴入封套內。然後將容有電池總成之封套 保持於3(TC之溫度至少經5分鐘之期間。此升高之溫度 加強共聚物層表面之丙酮溶合。 在冷卻至大氣溫度之後，電池總成從封套移出，然後真 空乾燥於6(TC 3小時確使任何丙酮殘量被除去。 -10- 552733 五、發明說明（9) 然後電池總成用塑化之液態電解質充入，其係由1莫耳 濃度LiBF4在溶劑中而構成，溶劑包含60.8 3 (重量 內酯，24.3 3%碳酸伸乙酯、12.16%碳酸甲氧基乙酯甲酯和 2.68%碳酸乙烯酯伸乙基酯。貯存16小時以確使電解質已 被所有電池總成零件所吸收。然後真空包裝於撓性包裝材 料內。如先前之電池，陽極和陰極兩者層積於此情形中之 多孔隔膜。 如此製成之電池經充電並陳化兩週，然後量測電容量如 上述。參考第2圖，表示對層積之電池在各種不同放電率 中電壓與電容量之變化，電池在2.75伏與4.25伏之問充 電和放電。對此特別之電池，在此情形中之額定電容量爲 約0.66安培小時。如上述之電池，在放電率增大時電容 量稍降，但是甚至在放電率爲2C時，可得之電容量約爲 額定電容之95%。 其將得以可用不同的液體使電池積層。例如，替代丙酮 ，液體可爲丙酮與碳酸二甲酯50:5 0(重量）之混合物，後 一成分本身並不作爲溶劑，而是用於溶劑的稀釋劑。由各 電極和微孔隔膜繞於一起而構成之電池總成，可以簡明浸 入此混合液體內，取出，並立即接受60°C之真空乾燥。 液體濕著於電池各零件之所有表面，且積層作用完成於如 前所述之程序。此程序免去使用密封封套，且已發現產生 相等之良好結果。 另一種適合之液體爲碳酸乙烯酯和碳酸二甲酯之混合物 ，其係用於60°C作爲共聚物之潛在溶劑。電池總成可被 -11- 552733 五、發明說明（1〇) 浸入此混合液體，取出，並立即接受60°C之真空乾燥以 層積成電池。 與其形成微孔共聚物層作爲分隔物，其爲可以代之以形 成於原位，例如直接鑄於陽極或陰極之表面上。以此狀況 ，該層可以甚至更薄，因爲不必予以操持。該層可爲例如 1微米厚，且可以在厚度中有少許不均勻，實際上，在陽 極或陰極表面中不均勻性之結果可能是共聚物層中之巨觀 孔洞。參考第3圖，其中表現（大約爲全尺寸）一卷電極材 料，其上已鑄有薄的共聚物膜。材料寬度爲10厘米，其 可被發現膜之大部份爲白色，指出其爲微孔性，但是在較 深色點之處，膜爲比較薄或不存在者。 變更之微孔共聚物層可以噴鍍於電極表面而形成。參考 第4圖，其中表示（大約爲全尺寸）之一卷電極材料，在其 上共聚物材料已被噴鍍形成間斷之層。白點指出至少在膜 上經噴鍍之區域爲微孔性。 由稍早所述製成之電池而用直接形成於電極表面之共聚 物層者，如第3和4圖所示，已被發現其所具電性實質上 與對應於第1圖和第2圖較早所述者相同。 -12-552733 V. Description of the invention (7) The cathode of the battery assembly is sandwiched between two thin layers of copolymers, so that each side is completely covered. Each component is placed between the release paper so that a roller of 20 Newton pressure is generated in the press. The wheels are pressed at a temperature of 120 ° C. The parts are thus laminated together. The anode is also sandwiched between thin layers of copolymer and laminated in the same way. The battery assembly is wound by a porous separator with a thickness of 20 microns to separate the anode and cathode. Each of these battery assemblies was enclosed in a sealed envelope made of an aluminum / plastic laminate, and a small amount of acetone was sprayed into the envelope at 0.5 g. The envelope containing the battery assembly is then maintained at a temperature of 30 ° C for at least 5 minutes. This elevated temperature strengthens the solvation (solvent) of the surface of the copolymer layer with acetone. After cooling to atmospheric temperature, the battery assembly was removed from the envelope, and then vacuum-dried at 60 ° C for 3 hours to ensure that all acetone residues were removed. Then, the battery assembly is vacuum-filled with a plasticized liquid electrolyte, for example, 1 mol of LiPF6 in a mixture of ethyl carbonate / ethyl carbonate. After storage for 16 hours, the electrolyte has been absorbed by all battery parts, and then vacuum-packed in a flexible packaging material. It has been found that the anode and the cathode are laminated to the porous separator. Obviously, the copolymer layer is fully adhered at 3 ° C and the copolymer layer is fully adhered to the porous separator. Because the lamination takes place outside Under the application of pressure, there is no risk of the porous separator breaking. Surprisingly, local fusion does not affect the porosity of each copolymer layer, and the entire procedure does not affect the porosity of the separator. The battery has good electrical properties. For example, referring to Figure 1, it shows the lightning pressure and electricity of the battery of the present invention 552733 V. Description of the invention (8) Capacity, for various changes in the discharge rate, the battery is charged and discharged at Between 2.75 volts and 4.25 volts. The rated battery capacity is the capacity at the discharge current (amperes), which is equal to one fifth of the battery capacity (ampere hours); this discharge is considered to be at C / Discharge at a ratio of 5. The rated battery capacity is determined by the first five discharge and recharge cycles, which is an estimate made at the C / 5 ratio. Then get the figure 1 It will be seen that the discharge capacity of this special battery is about 0.62 amp-hours; the capacity decreases slightly when the discharge rate increases, but even when the discharge rate is 2 C, the available capacity is about 0 · 5 2 amp hours, which is about 84% of the rated capacity. Although the active insert in the cathode of the modified battery is in this case Li Co 02 (obtained from FMC), the anode and cathode are made of the same as above Method. As before, the two electrodes are double-sided. Then each electrode is sandwiched between two thin layers of microporous copolymer (as described above) and laminated between the rollers at an elevated temperature , As in the previous example. Then the battery assembly was burned with a microporous polyethylene film with a thickness of 16 microns to separate the anode and the cathode. This separator was supplied by Tonen C hemica 1 C Orp. Each such battery The assembly is packed in a sealed envelope, and a small amount, such as 0.5 g of acetone, is sprayed into the envelope. Then the envelope containing the battery assembly is maintained at a temperature of 3 ° C for at least 5 minutes. This elevated temperature Strengthen acetone fusion on the surface of the copolymer layer. After cooling to atmospheric temperature, the battery assembly is removed from the envelope, and then vacuum-dried at 6 (TC for 3 hours to ensure that any remaining acetone is removed. -10- 552733 V. Description of the invention (9) Then the battery assembly is plasticized. Charged with liquid electrolyte, which is composed of 1 Molar concentration of LiBF4 in a solvent, the solvent contains 60.8 3 (by weight lactone, 24.3 3% ethyl ethyl carbonate, 12.16% methoxy ethyl methyl carbonate, and 2.68% carbonic acid Vinyl Ester and Ethyl Ester. Store for 16 hours to make sure that the electrolyte has been absorbed by all battery assembly parts. Then vacuum package in flexible packaging material. As in previous batteries, both the anode and cathode are laminated in this case. Porous membrane. The battery thus produced was charged and aged for two weeks, and the electric capacity was measured as described above. Referring to Figure 2, the voltage and capacity changes of the laminated battery at various discharge rates are shown. The battery is charged and discharged at 2.75 volts and 4.25 volts. For this particular battery, the rated capacity in this case is about 0.66 amp-hours. As for the above batteries, the capacity decreases slightly when the discharge rate increases, but even when the discharge rate is 2C, the available capacitance is about 95% of the rated capacity. It will enable the battery to be laminated with different liquids. For example, instead of acetone, the liquid may be a 50:50 (by weight) mixture of acetone and dimethyl carbonate. The latter component is not a solvent per se, but a diluent for the solvent. The battery assembly consisting of the electrodes and the microporous membrane wound together can be simply immersed in this mixed liquid, taken out, and immediately subjected to vacuum drying at 60 ° C. The liquid wets all the surfaces of the battery parts, and the lamination is performed in the procedure described above. This procedure eliminates the need for a sealed envelope and has been found to produce equivalent good results. Another suitable liquid is a mixture of ethylene carbonate and dimethyl carbonate, which is used as a potential solvent for copolymers at 60 ° C. The battery assembly can be -11- 552733 V. Description of the invention (1) Immerse this mixed liquid, take it out, and immediately accept vacuum drying at 60 ° C to laminate into a battery. Instead of forming a microporous copolymer layer as a separator, it can instead be formed in situ, for example, directly cast on the surface of an anode or a cathode. In this case, the layer can be even thinner because it does not have to be manipulated. This layer may be, for example, 1 micron thick, and may be slightly uneven in thickness. In fact, the result of the unevenness in the anode or cathode surface may be macroscopic holes in the copolymer layer. Refer to Figure 3, which shows a (approximately full size) roll of electrode material with a thin copolymer film cast thereon. The width of the material is 10 cm, and most of the film can be found to be white, indicating that it is microporous, but where the darker spots are, the film is thinner or non-existent. The modified microporous copolymer layer can be formed by spray coating on the electrode surface. Referring to Figure 4, there is shown (approximately full size) a roll of electrode material on which the copolymer material has been sprayed to form a discontinuous layer. White dots indicate that at least the sprayed area on the film is microporous. As shown in Figs. 3 and 4, a copolymer layer formed directly on the electrode surface from a battery made earlier is found to have substantially the same electrical properties as those corresponding to Figs. 1 and 2 The figure described earlier is the same. -12-