1234305^ 五、發明說明（1) ___^_ 【务明所屬之技術領域】 =發明係關於鋰二次電池，特別係關於 1隔離膜及使用該隔離膜之鋰二次電池。、種鋰二次電 【先前技術】 鋰二次電池由於其具有高能量密度、高帝 •:良特⑷6破廣泛應用於移動電話 =低自 寺4費性電子產品中。 聿5己本電腦 心;=次;:屬包括: = 卜離子電池及 鋰化合物為負極材料，：過渡金屬化合= ^解丁1〇2，Mn〇2)作為正極活性物質，m〇13，MoS2， 電池係於鐘金屬二：：逆進订的一類電池之總稱，·鋰：公 新概念之二次電池，；：=之基礎上發展起來的： 材料作為負極，以鐘^讀電池以人造石墨或天秋石累種全 極材料，以盔水右嬙鈷、鋰鎳、鋰錳等金屬氣;w寻石炭 λ相 …水有機落劑作a +糾 > 乳化物作a τ 兩頌，-類係電極為古乍為电知液。高分子鋰哈、：為正 電解液為固態或膠態=义子材料之經離子電池，二^包括 鋰二次電池均^σ物之鋰離子電池。 —$係 、n;要求電池内部不ί t τ機溶劑或有機聚人物 活潑性，鋰金不3水分子，因為u物作為 爆炸；另，水分觸會發生劇烈化學=具有高化學 降低：二次電池：；用電=反應，導致鐘電。電， ㈤，電池製程中=了命。 兒池毒化， 耗嚴格控 ---- '"衣二軋相對濕度f 度小於〇· 〇n $ 4頁 1234305 五、發明說明（2) (即D e w p〇i n t二-5 6 °C )。惟，控製空氣相對濕度小於 0. 0 4%需要高成本，且仍然無法避免製程中殘留一定量之 水分子。另，鋰二次電池在長期使用後，也無法避免水分 子氣滲透，導致電池功能喪失或電池安全性問題。 【内容】 本發明之目的係提供一種強吸水性之鋰二次電池隔離 膜。 本發明之另一目的係提供一種含有上述隔離膜之鋰二 次電池。 本發明提供一種鋰二次電难隔離膜，其中該隔離膜至 少包括一強吸水材料-高分子複合材料層，該層以高分子 材料為骨架’強吸水材料分散於其中5南分子材料與強吸 水材料之重量比為1 : 4〜3 : 4。其中強吸水材料包括分子 篩，具有露點低於-5 6 °C之強吸水性。高分子材料為有機 聚合物。 本發明還提供一種含有上述隔離膜之鋰二次電池。 與先前技術相較，本發明提供之隔離膜具有以下_優一 點：強吸水材料添加於隔離膜中，能完全吸附鋰二次電池 製程中殘留或使用時滲入之水分，降低電池製備成本，防 止電池使用過程中鋰離子電池中毒或鋰金屬二次電池中鋰 金屬與水發生劇烈反應，從而延長鋰二次電池之使用壽 命。另’強吸水材料按雜於向分子材料中，能增強隔離膜 機械強度，可減少鋰二次電池輾壓製程中電極穿插現象或 多次充放電後鋰金4屬針狀物產生導致之穿插現象，從而提1234305 ^ V. Description of the invention (1) ___ ^ _ [Technical field to which Mingming belongs] = The invention relates to a lithium secondary battery, and particularly to a separator and a lithium secondary battery using the separator. Lithium secondary batteries [Prior technology] Lithium secondary batteries are widely used in mobile phones = low-cost, low-cost electronic products because of their high energy density and high power.聿 5 computer computer; = times ;: genus includes: = ion batteries and lithium compounds as negative electrode materials ,: transition metal compound = ^ solution but 〇2, Mn〇2) as the positive electrode active material, m〇13, MoS2, the battery is based on Bell Metal II: the general name of the first-class battery that is reverse-ordered, lithium: the secondary battery of the new concept, and: developed on the basis of: material as the negative electrode, and the battery Synthetic all-polar materials made of artificial graphite or celestial stone, metal helmets such as scopolite, lithium nickel, lithium manganese, etc .; w look for the carbon lambda phase ... water organic agent as a + rectifier> a emulsifier as a τ two Som, the type of electrode is Gucha as the electrolyzed liquid. High polymer lithium: is a positive ion electrolyte battery is a solid or colloidal = lithium ion battery, and lithium ion batteries include lithium secondary batteries. — $ 系 、 n; It is required that the inside of the battery is not active, and lithium gold does not contain 3 water molecules, because the U substance acts as an explosion. In addition, the water will undergo severe chemistry = high chemical reduction: two Secondary battery :; electricity = reaction, leading to clock electricity. Electricity, alas, battery manufacturing process = dead. Children's pond poisoning, strict control of consumption-'" Relative humidity f of the second garment is less than 〇 · 〇n $ 4 pages 12343305 5. Description of the invention (2) (ie Dewpint 2-5 6 ° C) . However, controlling the relative humidity of the air to less than 0.4% requires high costs, and it is still impossible to avoid a certain amount of water molecules remaining in the process. In addition, after long-term use, lithium secondary batteries cannot avoid the penetration of moisture and gas, leading to loss of battery function or battery safety issues. [Content] The object of the present invention is to provide a lithium secondary battery separator with strong water absorption. Another object of the present invention is to provide a lithium secondary battery containing the above-mentioned separator. The invention provides a lithium secondary electrical difficult isolation film, wherein the isolation film includes at least a strong water-absorbing material-polymer composite material layer, and the layer uses a polymer material as a framework, and the strong water-absorbing material is dispersed therein. The weight ratio of the water-absorbing material is 1: 4 to 3: 4. Among them, strong water-absorbing materials include molecular sieves, which have strong water absorption with dew point lower than -5 6 ° C. The polymer material is an organic polymer. The present invention also provides a lithium secondary battery containing the above-mentioned separator. Compared with the prior art, the isolation film provided by the present invention has the following advantages: a strong water-absorbing material is added to the isolation film, which can completely absorb the moisture remaining in the lithium secondary battery during the manufacturing process or infiltrated during use, reducing the cost of battery preparation and preventing Lithium-ion battery poisoning or lithium metal secondary battery reacts violently during use of the battery, thereby prolonging the service life of the lithium secondary battery. In addition, the strong water-absorbing material is mixed with the molecular material, which can enhance the mechanical strength of the separator, reduce the electrode penetration phenomenon during the lithium secondary battery rolling process, or the lithium gold 4 metal needles caused by repeated charging and discharging. Phenomenon
第5頁 1234305Page 5 1234305
五、發明說明（3) 高鋰二次電池安全性。 【實施方式】 伞嘴、听貫施例一之鋰 請爹閱第 、一〜虹一— 人電池隔離膜 1 24包括一強吸水性材料-高分子複合材料層，該芦、一肤 子材料1 2為骨架，強吸水性材料分散於其中，=二以高分 1 2與強吸水性材料之重量比為丨：4〜3 ·· 4。強吸刀子材料 有路點低於-56 °C之強吸水性，優選為分子篩丨丨。二竹^ 1 了以為、/弗石分子師、碳分子篩，但不限於此， 布 水性即可，優選為3A分子筛，粒度範圍為1〇奈米二有強吸 =。隔離膜之骨架為高分子材料丨2，該高分子 ^ 、聚合物，如聚乙烯、聚丙烯、聚甲基丙烯酸甲酽、二 埽、聚乙二醇二丙稀酸S旨、聚乙婦。各烧嗣、聚』二二/乙 、布或其所構成之群組，但不限於此。 一 公如本發明之鋰二次電池隔離膜1 2 4之製備可以採用任何 ♦已知製備链二次電池隔離膜之方法。 離膜之製備方法包括以下步驟：法……亥隔 首先提供製備隔離膜用的高分子材料丨2及分 一，- 亚將分子篩進行物理性微細化，使1 米範圍内。 便其粒偟在1〇奈米〜10微 ^ f次將高分子材料12溶解於有機溶劑。有彳為丙 二但不限於此。高分子材料在溶液中質量濃度為5 高分子材料1 2與分子篩 °亥〉谷液經過充分混合後 然後向溶液中加入分子篩1 1 在溶液中之重量4比為1 : 4〜3 : 4。 1234305 五、發明說明（4) 成為均勻漿體。 再將漿體塗在PET膜基片上成為濕薄膜。將濕薄膜於 1 2 0 °C下乾燥1 5分鐘，再將薄膜於乾燥環境中浸泡於電解 液中3 0秒鐘後取出，用濾紙吸去膜表面之液體。 請參閱第二圖，本發明實施例一之鋰二次電池1 2 0包 括殼體1 2 1、正極1 2 2、負極1 2 3、有機電解液（圖未標示） 及本發明所提供之隔離膜1 2 4。 正極1 2 2之材質主要有過度金屬氧化物或硫化物，優 選為經锰、鋰錄、經始或經叙氧化物。 負極1 2 3對於鋰離子電池及高|分子鋰電池主要有碳材 料，包括石墨、碳粉、碳纖維或碳奈米管。另外，某些過 度金屬或其氧化物亦可選用，如錫及其氧化物。鋰金屬二 次電池之負極為鋰或鋰合金。 有機電解液包括碳酸異丙烯酯、碳酸亞乙酯、碳酸亞 丁酯、碳酸二甲醋、碳酸二乙酯、碳酸甲乙酯、1，2 -二甲 氧基乙烷或其所構成之群組。 電池殼體1 2 1包括金屬、合金、塑料或其組合。_ 一 本發明的經二次電池可具有任何形狀，如圓柱狀、棱 柱狀、片狀或鈕扣狀。 本發明之鋰二次電池之製備可採用任何公眾已知之製 備鋰二次電池之方法。具體而言，一種常用之方法包括於 殼體121内放置通過隔離膜124耦合之正極122及負極123， 隨後往其中注入電解質並將其密封。優選真空注射作為注 射電解質之方法，在對其無特別限製。亦可將耦合之電極V. Description of the invention (3) High lithium secondary battery safety. [Embodiment] Umbrella mouth, listen to the lithium in Example 1, please read the first, first ~ Hongyi-human battery isolation film 1 24 includes a strong water-absorbing material-polymer composite material layer, the reed, a skin material 1 2 is a skeleton, and a highly water-absorbent material is dispersed therein, and a weight ratio of 2 to a high score 1 2 and the strong water-absorbent material is 丨: 4 to 3 ·· 4. Strong suction knife material has strong water absorption with waypoint below -56 ° C, preferably molecular sieve. Erzhu ^ 1 thought, / Fu Shi molecular division, carbon molecular sieve, but is not limited to this, water distribution is sufficient, preferably 3A molecular sieve, particle size range of 10 nanometers and strong absorption =. The skeleton of the isolation membrane is a polymer material. The polymer ^ and polymers such as polyethylene, polypropylene, polymethylmethacrylate, difluorene, polyethylene glycol dipropionic acid, and polyethylene . Each burned, poly "22 / B, cloth, or the group formed by it, but not limited to this. The lithium secondary battery separator 1 2 4 as in the present invention can be prepared by any of the known methods for preparing chain secondary battery separators. The preparation method of the separation membrane includes the following steps: Method ... Firstly, the polymer material for preparing the separation membrane is provided. The molecular sieve is physically refined to a range of 1 meter. Dissolve the polymer material 12 in an organic solvent at 10 nm to 10 micron times. You are the second but not limited to this. The polymer material has a mass concentration of 5 in the solution. The polymer material 12 and the molecular sieve are mixed thoroughly. Then the molecular sieve 1 1 is added to the solution, and the weight 4 ratio in the solution is 1: 4 to 3: 4. 1234305 V. Description of the invention (4) Become a homogeneous slurry. The slurry is then coated on a PET film substrate to form a wet film. The wet film was dried at 120 ° C for 15 minutes, and then the film was immersed in the electrolytic solution in a dry environment for 30 seconds and then taken out, and the liquid on the surface of the film was blotted with filter paper. Please refer to the second figure. The lithium secondary battery 1 2 0 according to the first embodiment of the present invention includes a case 1 2 1, a positive electrode 1 2 2, a negative electrode 1 2 3, an organic electrolyte (not shown in the figure), and Isolation film 1 2 4. The material of the positive electrode 1 2 2 is mainly an excessive metal oxide or sulfide, and preferably it is manganese, lithium, warp or warp oxide. Negative electrodes 1 2 3 For lithium-ion batteries and high-molecular lithium batteries are mainly carbon materials, including graphite, carbon powder, carbon fiber or carbon nanotubes. In addition, some super metals or their oxides may be used, such as tin and its oxides. The negative electrode of a lithium metal secondary battery is lithium or a lithium alloy. Organic electrolytes include isopropenyl carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, 1,2-dimethoxyethane, or groups thereof . The battery case 1 2 1 includes a metal, an alloy, a plastic, or a combination thereof. _ A The secondary battery of the present invention may have any shape, such as a cylindrical shape, a prism shape, a sheet shape, or a button shape. The lithium secondary battery of the present invention can be prepared by any publicly known method for preparing a lithium secondary battery. Specifically, a commonly used method includes placing a positive electrode 122 and a negative electrode 123 coupled through a separator 124 in a casing 121, and then injecting an electrolyte therein and sealing it. Vacuum injection is preferred as a method for injecting the electrolyte, and there is no particular limitation on it. Coupling electrode
1234305 五、發明說明（5) 122、123在置於叙體j 2 1内之别用電解質溶液進行浸潰。 本發明實施例/提供P種具有雙層結構之隔離膜224 及使用該雙層結構隔離膜之鋰二次電池2 2 0〕。實施例二與 實施例一不同之處在於該隔離膜2 2 4還包括一低熔點有機 聚合物層1 3，該有機聚合物層1 3形成於強吸水材料—高分 子複合材料層之一表^面。有機聚合物優選為聚乙烯。 本發明實施例三/提供一種具有三層結構之隔離膜324 ^使用該三層結構隔離膜之鋰二次電池3 2 〇。實施例三與 貫施例一不同之處在於隔離膜3 24為三層結構，包括一層 =含強吸水材料之多孔低熔點有機聚合物膜丨3及一對強吸 ^^料―高分子複合材料膜，不含強吸水材料之多孔低熔 胺機聚合物膜1 3位於一對強吸水材料-高分子複合材料 、=間二其中多孔低熔點有機聚合物膜1 3優選為聚乙烯多 ρ籬腹田包池使用溫度超過11 0 °C時該多孔膜融化，堵住 ^ 隹勝孔，關斷電池正負極之間通路，防止電池内部短 明，^ ^強吸水材料本發明實施例均採用分子篩作詳-細一說 料均；域技術人員應當知道，其他具有強吸水性的材 粉體等。 兒见丨同離膜，如矽膠顆粒、活性氧化鋁 於RI:::提：：：離膜具有以下優點：強吸水材料添加 X . . v此兀王吸附鐘二次電池製程中殘留或使用時 ◊八之水分，降低雷、冰制 離子電池中毒戍鋰全屬衣傷成本，防止電池使用過程中裡 屬二次電池中鋰金屬與水發生劇烈反1234305 V. Description of the invention (5) 122, 123 are impregnated with electrolyte solution before they are placed in the narrative j 2 1. Embodiments of the present invention / provide P kinds of separators 224 having a double-layer structure and lithium secondary batteries 2 2 0 using the double-layer structure]. The difference between the second embodiment and the first embodiment is that the isolation film 2 2 4 further includes a low-melting-point organic polymer layer 13, and the organic polymer layer 13 is formed on one of the strong water-absorbing material-polymer composite material layer. ^ Surface. The organic polymer is preferably polyethylene. The third embodiment of the present invention / provides an isolation film 324 having a three-layer structure ^ A lithium secondary battery 3 2 0 using the three-layer structure isolation film. The difference between the third embodiment and the first embodiment is that the isolation film 3 24 has a three-layer structure, including one layer = a porous low-melting organic polymer film containing a strong water-absorbing material, and a pair of strong absorption materials-polymer composites. Material film, porous low-melting amine polymer film without strong water-absorbent material 1 3 is located in a pair of strong water-absorbent material-polymer composite material, among which the porous low-melting organic polymer film 1 3 is preferably polyethylene polyρ When the use temperature of the fence belly field pond exceeds 110 ° C, the porous membrane melts, blocks ^ 隹 sheng holes, shuts off the path between the positive and negative electrodes of the battery, and prevents the short and bright inside of the battery. ^ ^ Strong water-absorbing materials Molecular sieves are used for details-the materials are evenly described; those skilled in the art should know that other materials with strong water absorption properties and the like. See the same separation film, such as silica particles, activated alumina in RI :::::: The separation film has the following advantages: strong water-absorbing material is added X.. V This Wuwang adsorption residual or secondary battery manufacturing process The moisture content of the battery reduces the poisoning cost of thunder and ice ion batteries. Lithium is a cost of clothing damage and prevents the lithium metal and water in the secondary battery from reacting violently during battery use.
1234305 五、發明說明（6) 應，從而延長鋰二次電池之使用壽命。另，強吸水材料摻 雜於高分子材料中，能增強隔離膜機械強度，可減少鋰二 次電池輾壓製程中電極穿插現象或多次充放電後鋰金屬針 狀物產生導致之穿插現象，從而提高鋰二次電池安全性。 綜上所述，本發明確已符合發明專利之要件，遂依法 提出專利申請。惟，以上所述者僅為本發明之較佳實施 例，自不能以此限製本案之申請專利範圍。舉凡熟悉本案 技藝之人士援依本發明之精神所作之等效修飾或變化，皆 應涵蓋於以下申請專利範圍内。 411234305 V. Description of the invention (6) It should extend the service life of the lithium secondary battery. In addition, the strong water-absorbing material is doped in the polymer material, which can enhance the mechanical strength of the separator and reduce the phenomenon of electrode penetration during the lithium secondary battery rolling process or lithium metal needles caused by multiple charge and discharge. Thereby, the safety of the lithium secondary battery is improved. In summary, the present invention has indeed met the requirements for an invention patent, and a patent application was filed in accordance with the law. However, the above is only a preferred embodiment of the present invention, and it cannot be used to limit the scope of patent application in this case. All equivalent modifications or changes made by those skilled in the art of the case with the aid of the spirit of the present invention shall be covered by the scope of the following patent applications. 41
第9頁 1234305 圖式間单說明 第 一 圖 係 本 發 明 實 施 例一 圖 〇 第 二 圖 係 本 發 明 實 施 例一 圖 〇 第 二 圖 係 本 發 明 實 施 例二 圖 〇 第 四 圖 係 本 發 明 實 施 例二 圖 0 第 五 圖 係 本 發 明 實 施 例三 圖 〇 第 六 圖 係 本 發 明 實 施 例三 圖 〇 [ 主要 元 件 符 號 說 明 ] 分 子 篩 高 分 子 材 料 低 熔 點 有 機 聚 合 物 多 孔膜 殼體 正極 負極 隔離膜 鋰二次電池隔離膜結構示意 鋰二次電池内部結構示意 鋰二次電池隔離膜結構示意 鋰二次電池内部結構示意 鋰二次電池隔離膜結構示意Page 91234345 The drawing shows the first diagram of the first embodiment of the present invention. The second diagram is the first embodiment of the present invention. The second diagram is the second embodiment of the present invention. The fourth diagram is the embodiment of the present invention. The second figure 0 The fifth figure is the third embodiment of the present invention. The sixth figure is the third embodiment of the present invention. [Description of the main component symbols] Molecular sieve polymer material Low melting point organic polymer porous membrane shell Positive negative electrode separator Lithium Schematic illustration of the structure of the secondary battery isolation film. Schematic illustration of the internal structure of the lithium secondary battery. Schematic illustration of the internal structure of the lithium secondary battery. Schematic illustration of the internal structure of the lithium secondary battery.
I 鋰二次電池内部結構示意 11 12 13 121，221，321 1 2 2,2 22,3 2 2 123, 223, 323 1 2 4, 2 24, 324I Illustration of the internal structure of lithium secondary batteries 11 12 13 121, 221, 321 1 2 2, 2 22, 3 2 2 123, 223, 323 1 2 4, 2 24, 324
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