544969 五、發明說明（1 ) 本發明關係一種用於鋰離子電池內之電解質，和倂用 此電解質之電化學電池。 多年來已知使用鋰金屬陽極和其中可以夾插鋰離子之 材料所成之陰極而製成電池。此種電池可用一種在諸如 碳酸伸丙酯之有機溶劑中的鋰鹽溶液作爲電解質，並用 諸如濾紙或聚丙烯作爲分隔器。在第二或可再充電之鋰 電池之情況中，用鋰金屬陰極者因發生枝蔓結晶之生長 問題而未令人滿意，但使用諸如石墨之夾入材料卻可製 成令人滿意之電池。此種電池因爲鋰離子在充電和放電 之際交換於兩夾入材料之間而被視爲「鋰離子」電池或 「搖盪」電池。電池之電性，尤其關於循環壽期，有明 顯程度取決於電解質溶劑之選擇。 如Gozdz等人（US 5 296 3 1 8)所述，凝膠或固體電解 質可以製自於75至92 %偏二氟乙烯和8至25%六氟丙 烯所成之共聚物，其爲被溶解於諸如四氫呋喃之低沸點 溶劑係同鋰鹽和一種諸如碳酸伸乙酯/碳酸伸丙酯混合物 之助劑電解質溶劑，並以溶液鑄造而成。如此之電解質 只用具有極低熔融指數之均聚物聚偏二氟乙烯（PVdF)， 載於 GB 2 3 09 703 B(AE A Technology)。其亦可以首先 製成聚合物材料之多孔膜而後將膜浸入於鋰鹽在有機溶 劑內之溶液，使電解質溶液被聚合物膜吸收而製成’如 在ΕΡ0 730 316A(ElfAtochem)中所述。此等電解質，不 論製自鑄造或浸漬，具有凝膠或固體之外表，且在下文 視爲一種分離器。電池之電性，在此狀況中亦明顯受到 544969 五、發明說明（2 ) 電解質溶劑之選擇所影響。 在選擇方法中有許多思考堪稱可取。溶劑必須不與被 溶解之鋰鹽作化學反應，也不應與各電極有化學或電化 學之反應。在電池所被希求之操作範圍內應保持液態， 但應具有高沸點和高閃點以提高因過度充電之結果致使 電池發熱時之安全性。而且不應該太貴。尙無一種有機 流體經發現在各方面均爲理想者。 根據本發明而提供一種電解質，用於鋰離子電池，其 爲包含一陽極層和一陰極層，各含特定之鋰離子插入材 料，由分隔器分離，電解質含有T-丁內酯於10-80容積 %積圍內，碳酸伸乙酯於1-30容積％之範圍內，和至少 一種或爲乙烯基碳酸伸乙酯於1 -8容積％範圍內，或碳 酸甲氧基乙酯甲酯於8-80容積％範圍內。 雖然T -丁內酯（gBL)具備良好的電性，然其傾向與石 墨有電化學反應。碳酸伸乙酯（EC)能夠改善充電-放電效 率，並有助於形成鈍化層於石墨表面（其爲可被視爲一 種固體/電解質介面或SEI )。此種鈍化層阻止隨後之副 作用如電解質之還原作用。使用gBL與作爲溶劑之EC 之混合物而用於電池電解質爲已知，例如從〗？1〇-3 1 2 82 5 (Toshiba)，但是電池性質可藉加入本發明所規定 之其他成分而可提昇。 乙烯基碳酸伸乙酯（VEC)之存在較佳爲不多於5容積％ ，在形成低離子阻抗之鈍化層時爲特別有效。碳酸甲氧 乙基甲酯（ME MC)降低電解質之熔點，因而可以在較低 544969 五、發明說明（3) 之溫度使用電池。而且在電化學還原作用當中也相信 -〇C Η3基爲附著於溶劑分子之要角，能夠在石墨表面形 成SEI作爲緊密之薄膜。 電解質也可以含有碳酸氯二乙酯（C D E C)(亦即碳酸 1 -氯乙酯乙酯），較佳不多於5容積％，其亦有助於形 成鈍化層。對於使用此項材料之主要原因之一爲其可使 石墨材料可用gBL (和PC )循環。其亦對於具有高沸點 (1 5 9 -1 6 1 °C )和相對較高之閃點（6 5 °C )爲有益。電解質也 可含有碳酸三氟伸丙酯（TFPC)，可在最高80容積％之範 圍，其爲更能與石墨相容，與加入之陰極材料也少有反 應性。二氧化碳也可以溶於電解質內而有益，因如此將 有助於鈍化層之形成。 電解質也可以含有一種二碳酸酯如二碳酸二甲酯、二 碳酸二乙酯或二碳酸二-第三-丁酯，或二碳酸二-苯基亞 乙烯酯，在各種情形中不多於1 〇容積％，較佳爲約2% 。此等添加劑也能有助於保護電池免因過度充電而損毀 。例如如果電池電壓在4.3伏以上時不致冒煙或著火。 如此之電解質可用於與分離器結合，其如微孔性聚乙 烯，或微孔性之偏二氟乙烯基聚合物，在後一種情形中 形成凝膠或固體之電解質分離器。如wo〇 1 /48063所述 ，微孔性隔膜可由溶劑/非溶劑混合物鑄造’或由潛在溶 劑鑄造，使整個程序可以進行於無水或濕汽之中’減少 有水存在於最後之薄膜或隔膜內之風險（其爲對鋰離子 電池性質有害）。非溶劑不但應溶於溶劑’而且應實質 544969 五、發明說明（4) 上與溶劑可混合於所有之比例。非溶劑之沸點較佳爲高 於溶劑者，較佳約爲高於2 0 °C。例如溶劑可爲二甲基甲 醯胺或二甲基乙醯胺，依此情形則適合之非溶劑爲丨_辛 醇’其爲可溶於此等溶劑且其沸點爲約1 94。〇。 若干適於作爲溶劑和作爲潛在溶劑之液體而用於偏二 氟乙嫌基聚合物者列於各表。然而應了認知者並非所有 的溶劑均適合所有各等級之聚合物。 表1 溶劑 沸點/°c 四氫呋喃 6 6 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 80 140 酞酸二甲酯 110 280 在乾燥作用當中之蒸發速率不可太快，如果快速乾燥 易於產生巨孔，且亦可能導致形成不透氣皮層而妨礙其 下之液體蒸發。在使用潛在溶劑時，乾燥程序應進行於 低於潛在溶劑溶解溫度之溫度。結果聚合物沈澱，相信 發生二相··一爲富聚合物相’而一爲貧聚合物相。當潛 在溶劑蒸發時，富聚合物相之比例逐漸加大，但留存之 貧聚合物相滴粒使形成孔洞。 544969 五、發明說明（5) 本發明電解度適合用於有不同形狀範圍石墨和碳之陽 極，和有不同材料範圍之陰極。其可例如用於含有氧化 物LiCo02或LiNi〇2，或尖晶石氧化物LiMn204之陰極 ，陰極可以含有導電性物質如碳黑。電解質須有鹽溶解 於其中而提供離子傳導性，此種鹽例如爲LiPF6、LiBF4 、鋰醯亞胺（LiN(CF3S02)2)、鋰甲基化物（LiC(S02CF3)3) ，或雙草酸硼酸鋰（LiB(C204)2)，或此等鹽之混合物。 本發明茲以僅爲實施例者作進一步說明，並參考附圖 ，其中： 第1圖以曲線表示於不同的放電率，本發明電池電壓 隨充電之變化；和 第2圖以曲線表示在不同的放電率，本發明另一種電 池電壓隨充電之變化。 1 .非積層之電池 製成冬孔隔膜 具有低熔融指數値（在1 〇公斤和2 3 0。(：時小於0.7克 /10 分）之均聚物 PVdF ( Solvay 等級 6020 )，於 45°C 之溫度在攪拌中溶於N-甲基吡咯烷酮（WMP)，以1 5克 PVdF溶於85克NMP。然後逐滴小量加入9克之^辛醇 至聚合物溶液內’在加入時小心混合以保混合物均勻。 1 -辛醇之量不可太大’否則溶液成爲凝膠。然後混合混 合物於另2小時以保證其均勻性。所得三成分混合物用 醫師刮刀於輕輪上於錦箱基質而形成一初始厚度爲 0.25微米之層，然後通過具有兩個連續乾燥區分別爲65 544969 五、發明說明（6) °C和1 〇 〇 °C之7米長乾燥坑道。通過乾燥坑道之移動爲 0.5米/分。在各乾燥區內薄膜曝於1 4米/秒速度之乾燥 空氣氣流，除去蒸發之任何溶劑與非溶劑。乾燥空氣獲 自於使空氣通過除濕機，使其露點爲_4(TC。 於薄膜通過乾燥坑道當中，經歷1 4分鐘，溶劑和非 溶劑逐漸蒸發（雖然兩者均遠低於其沸點），溶劑傾向 於更快速而蒸發，因而獲得白色的聚合物隔膜，厚度約 2 0微米，用掃瞄電子顯微鏡分析表現其有微孔性。孔之 大小在0.5-2.0微米之範圍內，一般直徑約爲1微米， 至少在表面上爲如此。隔膜已被發現具有約爲53%之多 孑L度。 製造電極 陰極製自一混合物，包括Li Co 02 (獲自Nippon Chemical )，小比例之導電性碳，和作爲膠合劑之均聚 物PVdF 6020 (如上所述）等於N-甲基吡咯烷酮（NMP) 中之溶液。混合物用醫師刮刀在鋁箔上鑄造，並通過具 有例如爲80°C和120°C之溫度區域之乾燥器以確使NMP 之蒸發。然後重複此程序而產生雙面之陰極。隨後以真 空乾燥進一步確使全部NMP之除去。 陽極製自粒度爲1 0微米之消旋碳之微珠混合物，經 過在2 800°C熱處理者（MCMB 1 02 8 )，與小量之石墨、和 作爲膠合劑之均聚物PVdF 60 2 0於NMP中之溶液。此 混合物鑄造於銅箔上，以與上述相關於陰極之方式爲 之。 544969 五、發明說明（7) 電池總成 然後用厚度爲20微米之多孔隔膜分離陽極於陰極而 纏繞成電池總成。各個電池總成被入於一密封之鋁層積 物封套內，然後真空充入塑性液體電解質，例如爲1莫 耳濃度之 L i B F 4 於含 6 0 · 8 3 % g B L、2 4 · 3 3 % E C、1 2 . 1 6 % M EMC和2.6 8 %之VEC (均爲容積百分比）等之溶劑混 合物內。貯存1 6小時確使電解質已被所有的電池零件 吸收後，然後真空包裝於撓性包裝材料內。 然後充電於電池，陳化兩週，再接受五次放電與充電 之循環，充、放電電流（安培）在C/5値（C代表電池 電容量之安培小時）之估計，用以決定電池電容量C， 此値視認爲是額定之電池電容量。已發現此等電池具有 〇 . 6 1安培小時之額定電容量。然後使電池放電於一範圍 內不同的放量電流。 茲參考第1圖，以曲線表示電池在不同之放電電流： C/5、C/2、C和2C，在放電當中電壓之變化。放電電流 大者，電池電壓較低。雖然電池在較高之放電電流時不 產生較小的電容量，但是甚至其在最高的放電電流2 C， 電容量仍高（約爲9 5 % )。 2 .戀F的層穑雷池構造 製成薄的共聚物層 兩薄的微孔共聚物層是製自於相似之方法，…種 PVdF/GHFP (偏二氟乙烯和0%重量之六氟丙烯）之共 聚物，其1 2重量％之溶液，製自於以1 2克共聚物溶於 544969 五、發明說明（8) 8 8克D M F。然後逐滴加入小量之卜辛醇至共聚物溶液 內。在加入當中小心混合以保混合物均勻’然後繼續攪 拌2小時。再以所得三成分混合物用醫師刮刀於輥輪上 鑄造於鋁箔基質上而成初始爲0.0 6毫米厚之一層’然後 確實乾燥如上述。 依此形成厚度約2微米之微孔性層’各孔洞與上述隔 膜者相似。 製成各電極 陽極和陰極製自與上述相同之方法’雖然在此情形中 在陰極內之LiCo02是由FMC公司提供。在兩種情形中 各電極均爲雙面。 電池總成 陰極被夾於兩片薄的共聚物層之間，使其各表面完全 被覆蓋，且此等零件以接受在兩輥輪所給予20牛頓之 壓迫力強於1 2 (TC之升高溫度，此時其係被置於離形紙 之間，而被層積於一起。 陰極亦被夾於兩片厚的共聚物層之間，以相同方法層 積於一起。 然後以厚度爲1 6微米之多孔聚乙烯隔膜分隔陽極與 陰極而纏繞成電池總成，隔膜由Τ ο n e η C h e m i c a 1公司供 給。各個如此之電池被容入一密封之鋁/塑膠層積物封套 ，並用如〇 · 5克之少量丙酮噴入於封套內。然後將裝有 電池之封套保持於3 0 °C之溫度至少5分鐘。此昇高之溫 度加強丙酮對於共聚物層表面之溶合作用。 -10- 544969 五、發明說明（9) 冷卻至大氣溫度後，從封套取出電池，然後真空乾燥 於60°C 3小時以確使任何殘存之丙酮已被除去。 然後以上述四成分之塑化液體電解質以真空充入於電 池總成，所用電解質爲1莫耳濃度之LiBF4在含有 60.83 % gBL、24.33 % EC、12.16% MEMC 和 2.68% VEC 之溶劑混合物內。貯存1 6小時確使電解質已被所有各 電池零件所吸收後，然後真空包裝於撓性包裝材料內。 已發現陽極和陰極兩者已積合於多孔隔膜。顯然此係 因爲各共聚物層在被丙酮局部溶合於3 0 °C時有足夠之黏 性而接著於多孔隔膜。因爲層積作用發生而無需外加壓 力，無使多孔隔膜穿破之虞。令人驚奇者爲局部溶合並 不影響各共聚物膜之多孔性，而且整個方法並不影響隔 膜之多孔性，使電池在加入塑化液體電解質後具有良好 電性。 使以此方式製成之電池充電，並陳化兩週’然後景測 其電容量如前述。參考第2圖’其中表示積層電對於各 種不同的放電率中電壓對電容量之變化。電池是在2.7 5 伏與4.25伏之間充、放電。對於此特別之電池在此情形 中之額定電池電容量約爲0.6 6安培小時。以如上所述之 電池而言，電容量稍爲降低於放電率增大’但是甚至在 放電率爲2 C之時，所得電容量約爲額定電容量之 9 5% 〇 將受肯定者爲此型積層電池可以配合不同的微孔分隔 器以代替聚乙烯隔膜，例如6020 PVdF或1015 PVdF之 -11- 544969 五、發明說明（1〇) 微孔均聚物隔膜，製自與上述非積層電池相關之說明。 此兩均聚物P V d F均有極低的熔融指數：典型之數値獲 自於 2 3 0 °C 和 2 1 . 6 公斤·· S 0 L E F 1 0 1 5 ··在 2 · 8 與 4.6 克 /1 〇分之間；而SOLEF 6020 : $ 2克/1 0分，後者所量測 近乎可測之極限。均聚物之分子量分別爲240000與 3 0 0000。微孔性分隔器必須是一種不爲丙酮明顯溶合之 材料，其主要性在於其多孔性不受影響。 本發明之優點爲：（i)高沸點和高閃點電解質爲安全問 題所必需；和（Π)使用此電解質之電池之低脹大性。從 各圖中之放電曲線明顯得知非積層與積層兩種電池均有 良好的電性。 -12-544969 V. Description of the invention (1) The present invention relates to an electrolyte used in a lithium ion battery, and an electrochemical cell using the electrolyte. It has been known for many years to use lithium metal anodes and cathodes made of materials capable of intercalating lithium ions to make batteries. Such a battery can use a lithium salt solution in an organic solvent such as propylene carbonate as an electrolyte, and a separator such as filter paper or polypropylene. In the case of a second or rechargeable lithium battery, a lithium metal cathode is unsatisfactory due to the growth of branch crystals, but a sandwich battery such as graphite can be used to produce a satisfactory battery. This type of battery is considered a "lithium-ion" or "swing" battery because lithium ions are exchanged between the two sandwiched materials during charging and discharging. The battery's electrical properties, especially with regard to cycle life, depend significantly on the choice of electrolyte solvent. As described by Gozdz et al. (US 5 296 3 1 8), gels or solid electrolytes can be made from a copolymer of 75 to 92% vinylidene fluoride and 8 to 25% hexafluoropropylene, which is dissolved Low-boiling solvents such as tetrahydrofuran are cast in solution with lithium salts and an auxiliary electrolyte solvent such as a mixture of ethyl carbonate / propylene carbonate. As such an electrolyte, only a homopolymer polyvinylidene fluoride (PVdF) having an extremely low melt index is used, as described in GB 2 3 09 703 B (AE A Technology). It can also be made into a porous membrane of a polymer material first, and then immersed in a solution of a lithium salt in an organic solvent so that the electrolyte solution is absorbed by the polymer membrane, as described in EP 0 730 316A (ElfAtochem). These electrolytes, regardless of whether they are cast or impregnated, have the appearance of a gel or solid, and are hereinafter referred to as a separator. The electrical property of the battery is also obviously affected by the choice of electrolyte solvent in this situation. There are many thoughts in choosing a method that are desirable. The solvent must not react chemically with the dissolved lithium salt, nor should it react chemically or electrochemically with each electrode. It should remain liquid within the operating range desired by the battery, but should have a high boiling point and a high flash point to improve the safety of the battery due to overcharging. And it should not be too expensive. No organic fluid has been found to be ideal in every respect. According to the present invention, there is provided an electrolyte for a lithium ion battery. The electrolyte includes an anode layer and a cathode layer, each containing a specific lithium ion insertion material, separated by a separator, and the electrolyte contains T-butyrolactone at 10-80. Within the volume% area, the ethylene carbonate is in the range of 1-30% by volume, and at least one of them is vinyl ethylene carbonate in the range of 1-8% by volume, or the methoxyethyl carbonate is in the range of 1 to 8% by volume. 8-80% by volume. Although T-butyrolactone (gBL) has good electrical properties, it tends to have electrochemical reactions with graphite. Ethylene carbonate (EC) can improve the charge-discharge efficiency and help to form a passivation layer on the graphite surface (which can be considered as a solid / electrolyte interface or SEI). This passivation layer prevents subsequent side effects such as electrolyte reduction. It is known to use a mixture of gBL and EC as a solvent for battery electrolytes, such as from? 1〇-3 1 2 82 5 (Toshiba), but the battery properties can be improved by adding other ingredients specified in the present invention. The presence of vinyl ethylene carbonate (VEC) is preferably not more than 5% by volume, which is particularly effective when forming a passivation layer with low ion resistance. Methoxymethyl carbonate (ME MC) lowers the melting point of the electrolyte, so the battery can be used at a lower temperature of 544969 V. Description of the invention (3). In the electrochemical reduction, it is also believed that the -0C 基 3 group is the main corner attached to the solvent molecules, and can form SEI on the graphite surface as a compact film. The electrolyte may also contain chlorodiethyl carbonate (C D E C) (i.e., 1-chloroethyl carbonate), preferably not more than 5% by volume, which also helps to form a passivation layer. One of the main reasons for using this material is to make graphite materials available for gBL (and PC) cycling. It is also beneficial for those with a high boiling point (1 5 9 -1 6 1 ° C) and a relatively high flash point (65 ° C). The electrolyte may also contain trifluoropropane carbonate (TFPC), which can be in the range of up to 80% by volume, which is more compatible with graphite and has less reactivity with the cathode material added. Carbon dioxide is also beneficial because it can be dissolved in the electrolyte, which will help the formation of the passivation layer. The electrolyte may also contain a dicarbonate such as dimethyl dicarbonate, diethyl dicarbonate or di-third-butyl dicarbonate, or di-phenylvinyl dicarbonate, in each case not more than 1 0% by volume, preferably about 2%. These additives can also help protect the battery from damage caused by overcharging. For example, if the battery voltage is above 4.3 volts, it will not cause smoke or fire. Such an electrolyte can be used in combination with a separator, such as a microporous polyethylene, or a microporous vinylidene fluoride polymer, which in the latter case forms a gel or solid electrolyte separator. As described in wo〇1 / 48063, microporous membranes can be cast from solvent / non-solvent mixtures or from latent solvents, allowing the entire process to be performed in the absence of moisture or moisture. Internal risks (which are harmful to the nature of lithium-ion batteries). The non-solvent should not only be soluble in the solvent ', but also be substantially 544969. V. Description of the invention (4) It can be mixed with the solvent in all proportions. The boiling point of the non-solvent is preferably higher than that of the solvent, and is preferably higher than about 20 ° C. For example, the solvent may be dimethylformamide or dimethylacetamide. A suitable non-solvent in this case is octanol ', which is soluble in these solvents and has a boiling point of about 194. 〇. A number of suitable liquids for solvents and potential solvents for vinylidene fluoride polymers are listed in the tables. However, it should be understood that not all solvents are suitable for all grades of polymers. Table 1 Solvent boiling point / ° c Tetrahydrofuran 6 6 Methyl ethyl ketone 80 Dimethylformamide 153 Dimethylacetamide 166 Dimethylmethylene feng 189 N -Methylpyrrolidone 203 Table 2 Potential 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 80 140 Dimethyl phthalate 110 280 The evaporation rate during drying cannot be too fast. If fast drying is easy to produce macropores, it may also lead to the formation of a gas-tight skin layer and hinder the evaporation of the liquid below it. When using a potential solvent, the drying procedure should be performed at a temperature below the melting temperature of the potential solvent. As a result, the polymer precipitated, and it is believed that two phases occurred. One is a polymer-rich phase and the other is a polymer-lean phase. When the potential solvent evaporates, the proportion of the polymer-rich phase gradually increases, but the remaining particles of the polymer-poor phase cause pores to form. 544969 V. Description of the invention (5) The degree of electrolysis of the present invention is suitable for anodes having different shapes of graphite and carbon, and cathodes having different ranges of materials. It can be used, for example, in a cathode containing an oxide LiCo02 or LiNiO2, or a spinel oxide LiMn204. The cathode can contain a conductive substance such as carbon black. The electrolyte must have a salt dissolved in it to provide ion conductivity. Such salts are, for example, LiPF6, LiBF4, lithium ammonium (LiN (CF3S02) 2), lithium methylate (LiC (S02CF3) 3), or bisoxalate boric acid Lithium (LiB (C204) 2), or a mixture of these salts. The present invention is further described by way of example only, and with reference to the accompanying drawings, wherein: FIG. 1 is a graph showing different discharge rates, and the battery voltage of the present invention changes with charging; The discharge rate of another battery voltage of the present invention varies with charging. 1. A non-layered battery made of a winter-pored separator with a low melting index 値 (at 10 kg and 2 30. (: less than 0.7 g / 10 min) PVdF (Solvay grade 6020) homopolymer at 45 ° The temperature of C is dissolved in N-methylpyrrolidone (WMP) with stirring, and 15 g of PVdF is dissolved in 85 g of NMP. Then 9 g of octanol is added dropwise to the polymer solution in a small amount. Carefully mix when adding To ensure that the mixture is homogeneous. 1-The amount of octanol must not be too large, otherwise the solution becomes a gel. Then the mixture is mixed for another 2 hours to ensure its homogeneity. The resulting three-component mixture is doctor-bladed on a light wheel on the brocade substrate. Form a layer with an initial thickness of 0.25 microns, and then pass through a 7-meter-long drying tunnel with two continuous drying zones of 65,544,969. 5. Description of the invention (6) ° C and 100 ° C. The movement through the drying tunnel is 0.5 M / min. In each drying zone, the film is exposed to a stream of dry air at a speed of 14 meters per second to remove any solvents and non-solvents that evaporate. Dry air is obtained by passing air through a dehumidifier with a dew point of _4 ( TC. In the film through the drying tunnel, Over 14 minutes, the solvent and non-solvent gradually evaporate (although both are far below their boiling points). The solvent tends to evaporate more quickly, thus obtaining a white polymer membrane with a thickness of about 20 microns. Scanning electron microscope The analysis shows that it has microporosity. The size of the pores is in the range of 0.5-2.0 microns, and the diameter is generally about 1 micron, at least on the surface. The separator has been found to have a degree of L of about 53%. Manufacturing The electrode cathode is made from a mixture including Li Co 02 (obtained from Nippon Chemical), a small proportion of conductive carbon, and a homopolymer PVdF 6020 (as described above) equal to N-methylpyrrolidone (NMP). The mixture was cast on a foil with a doctor's spatula and passed through a dryer having a temperature range of, for example, 80 ° C and 120 ° C to ensure the evaporation of NMP. This procedure was then repeated to produce a double-sided cathode. Vacuum drying further removed all NMP. The anode was made from a mixture of microbeads with racemic carbon with a particle size of 10 microns, which had been heat treated at 2 800 ° C (MCMB 1 02 8), and a small amount of graphite, and as gum Solution of homopolymer PVdF 60 2 0 in NMP. This mixture was cast on copper foil in the manner related to the cathode described above. 544969 V. Description of the invention (7) The battery assembly is then used with a thickness of 20 A micron-sized porous separator separates the anode from the cathode and is wound into a battery assembly. Each battery assembly is enclosed in a sealed aluminum laminate envelope and then vacuum-filled with a plastic liquid electrolyte, for example, 1 mol of L i BF 4 In a solvent mixture containing 60.83% g BL, 24.33% EC, 12.16% M EMC and 2.6.8% VEC (both by volume). After storing for 16 hours to ensure that the electrolyte has been absorbed by all battery parts, it is vacuum packed in flexible packaging materials. Then charge the battery, age for two weeks, and then accept five cycles of discharge and charge. The charge and discharge current (ampere) is estimated at C / 5 値 (C represents the ampere-hour of the battery capacity) to determine the battery power. Capacity C, this contempt is considered to be the rated battery capacity. These batteries have been found to have a rated capacity of 0.61 amp hours. The battery is then discharged at different discharge currents within a range. With reference to Figure 1, the curves show the different discharge currents of the battery: C / 5, C / 2, C, and 2C. The voltage changes during discharge. The larger the discharge current, the lower the battery voltage. Although the battery does not produce a smaller capacity at higher discharge currents, even at the highest discharge current of 2 C, the capacity is still high (about 95%). 2. The layer of F is made of a thin copolymer layer and two thin microporous copolymer layers are made by a similar method, ... a kind of PVdF / GHFP (vinylidene fluoride and 0% by weight of hexafluoropropylene ) Copolymer, a 12% by weight solution, was prepared by dissolving 544969 with 12 grams of copolymer. V. Description of the invention (8) 8 8 grams of DMF. A small amount of butanol was then added dropwise to the copolymer solution. During the addition, carefully mix to keep the mixture homogeneous' and continue to stir for 2 hours. Then, the obtained three-component mixture was cast on an aluminum foil substrate with a doctor blade on a roller to form a layer having an initial thickness of 0.06 mm, and then dried as described above. Accordingly, each hole of the microporous layer 'having a thickness of about 2 m is similar to that of the above-mentioned separator. Fabrication of each electrode The anode and cathode were made by the same method as above 'although in this case LiCo02 in the cathode was provided by FMC Corporation. In both cases, each electrode is double-sided. The cathode of the battery assembly is sandwiched between two thin copolymer layers so that its surfaces are completely covered, and these parts are stronger than 1 2 (liters of TC) by the pressure of 20 Newtons given by the two rollers. High temperature, at this time it is placed between release paper and laminated together. The cathode is also sandwiched between two thick copolymer layers and laminated together in the same way. Then the thickness is A 16-micron porous polyethylene separator separates the anode and cathode and is wound into a battery assembly. The separator is supplied by Ton η Chemica 1. Each such battery is housed in a sealed aluminum / plastic laminate envelope and used For example, a small amount of 0.5 g of acetone is sprayed into the envelope. Then the battery-containing envelope is kept at a temperature of 30 ° C for at least 5 minutes. This increased temperature enhances the solvation of the acetone on the surface of the copolymer layer. 10- 544969 V. Description of the invention (9) After cooling to atmospheric temperature, remove the battery from the envelope, and then vacuum-dry at 60 ° C for 3 hours to ensure that any remaining acetone has been removed. Then use the above four-component plasticizing liquid The electrolyte is charged in a vacuum In the battery assembly, the electrolyte used is LiBF4 with a concentration of 1 mole in a solvent mixture containing 60.83% gBL, 24.33% EC, 12.16% MEMC, and 2.68% VEC. Storage for 16 hours ensures that the electrolyte has been used by all battery parts After absorption, it is then vacuum-packed in a flexible packaging material. It has been found that both the anode and the cathode have been integrated in the porous membrane. Obviously this is because each copolymer layer is adequate when it is locally dissolved at 30 ° C by acetone. It sticks to the porous membrane. Because lamination occurs without external pressure, there is no risk of breaking the porous membrane. The surprising thing is that local fusion does not affect the porosity of each copolymer film, and the entire method is not Affects the porosity of the separator, so that the battery has good electrical properties after the plasticized liquid electrolyte is added. The battery made in this way is charged and aged for two weeks. Then the capacitance is measured as described above. Refer to Figure 2 ' Among them, it shows the change of the voltage to the capacitance in the various discharge rates of the laminated battery. The battery is charged and discharged between 2.75 volts and 4.25 volts. For this particular battery, the The rated battery capacity is about 0.6 6 amp hours. For the battery as described above, the capacity is slightly reduced and the discharge rate is increased, but even when the discharge rate is 2 C, the obtained capacity is about the rated capacity 9 5% 〇 It will be affirmed that this type of laminated battery can be used with different microporous separators instead of polyethylene separators, such as 6020 PVdF or 1015 PVdF -11- 544969 V. Description of the invention (1〇) Microporous homopolymer Separator, made from the description related to the non-laminated battery described above. Both of these homopolymers PV d F have very low melting indices: typical numbers are obtained from 230 ° C and 2 1.6 kg · S 0 LEF 1 0 1 5 ·· Between 2 · 8 and 4.6 g / 10 minutes; and SOLEF 6020: $ 2 g / 10 minutes, the latter measurement is almost measurable limit. The molecular weights of the homopolymers are 240,000 and 300,000. The microporous separator must be a material that does not significantly dissolve in acetone. The main reason is that its porosity is not affected. The advantages of the present invention are: (i) high boiling point and high flash point electrolytes are necessary for safety issues; and (Π) low swelling properties of batteries using this electrolyte. It is clear from the discharge curves in the figures that both non-laminated and laminated batteries have good electrical properties. -12-