經濟部中央標率局負工消費合作杜印製 [工業應用範圍] 本發明係有關於電池隔板，其製備方法和使用該隔板的 非水性二次電池。其目的在於提供—種製備非水性二次電 池如薄且柔軟性與機械強度均突出之鋰二次電池之方法。 [先前技藝] 使用在Μ電池和其它此種非水性電池的隔板扮演的角色 是避免在正極和負極之間產生短路，以及藉由引人隔板的 許多孔洞留住電解質而確保導電性。至目前為纟，傳統的 隔板一直都是聚乙烯（ΡΕ)和聚丙晞（ΡΡ)的多孔薄膜、ρΕ 和ΡΡ貼在一起的二層薄膜、和ΡΕ夾在ρρ之間的三層薄 膜等。然而，ΡΕ和ΡΡ是易燃性材質，且特別是在鋰電池 中’需要有更高安全性之材質。 最近，已提出一種鋰電池，其使用作為隔板（大分子凝膠 電解免）的是偏一氟乙缔共聚物膜，此膜已由溶解原 文如此}或其它此種Li鹽於碳酸鹽溶劑中所形成的溶液泡 脹過[國内公告案*8-507407和8-509100]。在组構此種電池 時，係先製作包含偏二氟乙晞共聚物和可塑劑的膜，之 後’必須有一道複雜步驟’包括使用低沸溶劑從膜上將可 塑劑移除’或是更換電解質溶液。而且，用溶劑泡脹過的 偏二氟乙烯共聚物膜通常在高溫時（5 〇 °c和以上）耐溫性不 足，而在低溫時（0 t和以下），電池性質如電容量則會降 低。 再者，以包含聚偏二氟乙烯樹脂的多孔膜作為隔板使用 已被提出過（曰本未審查專利公開第8-25〇127號； -4 - 本紙張尺度適用中國國家標準（CMS ) A4規格（210χ297公釐} (诗先閲讀背面之注意事項再填寫本頁) 裝. 424347 A7 _________Β7 五、發明説明（VI ^ ^ ^Du printed by the Ministry of Economic Affairs of the Central Bureau of Standards and Labor Cooperation [Industrial Application Scope] The present invention relates to a battery separator, a preparation method thereof, and a non-aqueous secondary battery using the separator. The purpose is to provide a method for preparing a non-aqueous secondary battery such as a lithium secondary battery that is thin and has outstanding flexibility and mechanical strength. [Prior art] The role of separators used in M batteries and other such non-aqueous batteries is to avoid short circuits between the positive and negative electrodes, and to ensure conductivity by retaining the electrolyte through the many holes that attract the separator. Up to now, traditional separators have always been porous films of polyethylene (PE) and polypropylene (PP), two-layer films with pE and PP attached together, and three-layer films with pE sandwiched between pρ, etc. . However, PE and PP are flammable materials, and especially in lithium batteries, materials with higher safety are required. Recently, a lithium battery has been proposed, which is used as a separator (macromolecule gel electrolysis exemption) is a vinylidene fluoride copolymer film. This film has been prepared by dissolving the original} or other such Li salts in carbonate solvents. The solution formed in swelled [domestic bulletins * 8-507407 and 8-509100]. When constructing such a battery, a film containing a vinylidene fluoride copolymer and a plasticizer is first produced, and then 'complex steps must be included' including removing the plasticizer from the film using a low boiling solvent, or replacing it. a. In addition, the vinylidene fluoride copolymer film swelled with a solvent is usually insufficient in temperature resistance at high temperature (50 ° C and above), and at low temperature (0 t and below), the battery properties such as capacitance will be reduce. Furthermore, the use of a porous membrane containing polyvinylidene fluoride resin as a separator has been proposed (Japanese Unexamined Patent Publication No. 8-25〇127; -4-This paper size applies Chinese National Standard (CMS) A4 Specifications (210x297 mm) (Read the notes on the back of the poem before filling this page). 424347 A7 _________ Β7 V. Description of the Invention (VI ^ ^ ^
Toriyama等人，第37屆電池討論會摘要[Dai 37_kai Denchi T〇ronkai Koen Yoshishu]，第 2 頁，1996)。根據 這些參考文獻，聚偏二氣乙歸·樹脂係用有機電解質液體浸 脹（增塑），且因爲其中基質區域也貢獻離子導度，所以當 此多孔膜用作隔板時，可得到比使用聚乙烯或聚丙婦多孔 膜較大的離子導度。然而，在此種情況下，爲了有高離子 導度，需要使用具有高孔隙度之多孔膜，因此隔板的機械 強度就變成了問題。 [本發明欲解決的問題] 爲了解決傳統聚乙烯和聚丙烯多孔體，和大分子凝膠電 解貝的問喊’並得到一種機械強度和離子導度均突出之聚 偏二氟乙烯樹脂多孔體，研究的結果，本發明人等完成了 本發明。 [解決問題的方法] 本發明係有關於電池隔板，其特徵爲它包含聚偏二氟乙 晞樹脂多孔體’及分散於該多孔體中之無機填充物。 使用於本發明的”聚偏二氟乙烯樹脂"是熱塑性氟樹脂， 經濟部中央標率局員工消費合作社印製 含有至少5 0重量％，較佳至少有7 5重量％偏二氟乙烯， 作爲樹脂結構單位。因此，它不限於只包含偏二氟乙烯的 均聚物’也可以是偏二氟乙烯和一種或一種以上選自下列 單體的單體之共聚物。可共聚合的單體，舉例言之，有四 氟乙烯、三氟乙烯、三氟氣乙烯、氣乙烯、六氟丙烯、乙 晞和全氟烷基乙醚等s作爲聚偏二氟乙烯共聚合物，較佳 使用偏二氟乙烯和六氟丙烯的共聚物（六氟丙烯的含量不要 _ -5- 本纸張尺度適用中i國家標準公犮） ~~ ·~ A7 B7 五'發明説明（3 ) 超過15重量％ )。此種熱塑性聚偏二氟乙晞樹脂可用乳液 聚合法’懸浮聚合法和其它常用的聚合法獲得，且熔體流 動速率（MFR)値較佳是從〇. 〇〇5至1 〇〇克/ 1 〇分（在23 〇 °C及 2-16 kg負重下測得），更佳是從〇, 〇丨到2〇克八〇分。 在本發明中’每100重量份：聚偏二氟乙烯樹脂應加2 到200重量份，更佳5至5 0重量份..的無機填充物。 用於本發明的無機填充物，可使用高聚合物材料一般所 用的許多種類（參考，，，The Dictionary of Filler Application [Fira Katsuyo Jiten]"，Fira Kenkyukai 編輯，Taiseisha 發 行’ 1 994)。特定言之，較佳使用無機氧化物和矽酸鹽。無 機氧化物的實例有二氧化矽、氧化鋁、矽藻土 '氧化鈦、 氧化鈣、氧化鋅、氧化鎂、氧化錫、鐵酸鹽和其類似物。 這些之中’以分解方法製造出來的氧化鋁和氧化矽之使用 是特別佳的。再者，矽酸鹽的實例有矽酸鈣、滑石、雲 母、蒙脱石、膨潤土、海泡石、.imogolite 、絹雲母 (sericite) '玻璃纖維和玻璃小珠等。無機填充物的形狀沒 有特別地限制，且它可爲纖維狀、針狀、小板狀或粒狀。 經濟部中央榡準局員Η消費合作衽印繁 (請先閱讀背面之注意事項再填寫本頁) 再者’前述無機塡充物的表面可藉表面有羥基的官能基 (如矽醇（silano!)基），和矽拔化合物（如鹵矽故、燒氧基矽 坡、矽氮烷、矽氧烷和其類似物）反應而具疏水性。 本發明製作電池隔板的方法沒有特別地限制，可以使用 從高聚合物樹脂製造多孔體的已知方法。作爲傳統方法， 有一種方法稱之爲溶膠凝膠方法，其使用高聚合物樹脂和 非溶劑的溶液。明確言之，前述的無機填充物係分散於藉 _ '6 - 經濟部中央標準局員工消費合作牡印製 424347 A7 ______B7 五、發明説明（4 ) 由聚偏二氟乙烯樹脂溶解於溶劑中而獲得的溶液中，然後 藉由使此溶液與聚偏4乙烯樹脂的非溶劑接觸而得'多、孔 體。在此種情泥，用作爲容解聚偏二氟乙晞樹月旨的溶劑有 N-甲基-吡咯烷酮、甲醯胺、二曱基曱醯胺 '二甲基乙醯 胺、二曱亞礙、r - 丁内醋、四甲腺、鱗酸三甲醋、丙嗣、 曱基乙基酮、四氫呋喃和其類似物。而且，它們的混合物 也可用作爲容劑。溶液中含有聚偏二氟乙缔樹脂的濃度正 常地是從5到5〇重量％，較佳地是從1〇到3〇重量％。用 作爲不良溶劑，較佳使用水或醇類，以水特佳。 藉由使含有分散無機塡充物之聚偏二氟乙烯樹脂溶液（其 製備如上所述）與不良溶劑接觸，溶膠凝膠轉換立即開始， 並產生多孔體。在此情況下，接觸較佳應以不民溶劍進行 充分長的時間，以從多孔體中萃出溶劑，其係使用含有少 量落解聚偏二氟乙缔樹脂的溶劑的不良溶劑。此—接觸的 時間將根據多孔體的大小而異，但是，通常較佳至少】〇 秒，更佳至少3 0秒。 電池隔板所希望的多孔體形狀是膜。厚度較佳從5到2〇〇 微米，更佳從10到100微米。孔徑較佳不超過2〇微米’ 更佳從〇.〇5到〗〇微米。以孔隙性而言，5到85%爲較 佳，而5到8 0 %更佳。 本發明的多孔體也可以（如果需要的話）被拉伸（熱拉伸或 冷拉伸）或接觉一些處理、或者兩者，以提高結晶度或固定 結晶結構。拉伸比將根據樹脂的種類（分子量和共聚用單體 含量）和多孔體製造條件等而變，但將合適的爲從K1至 _ -7- 本紙張尺度適用中國國家標準了CNS ) Λ4規格（2丨0\ 297公_^~] ---------— (請先閱讀背面之注意事項再填寫本頁) 装' 、YaToriyama et al., Abstract of the 37th Battery Symposium [Dai 37_kai Denchi Torokai Koen Yoshishu], p. 2, 1996). According to these references, PVDF resins are swelled (plasticized) with an organic electrolyte liquid, and because the matrix region also contributes ion conductivity, when this porous membrane is used as a separator, the ratio can be obtained. Use polyethylene or polypropylene porous membranes for greater ion conductivity. However, in this case, in order to have a high ion conductivity, it is necessary to use a porous membrane having a high porosity, so that the mechanical strength of the separator becomes a problem. [Problems to be Solved by the Invention] In order to solve the conventional polyethylene and polypropylene porous bodies, and the question of macromolecular gel electrolytic shells, and obtain a polyvinylidene fluoride resin porous body with outstanding mechanical strength and ionic conductivity As a result of the research, the present inventors have completed the present invention. [Solution to Problem] The present invention relates to a battery separator, which is characterized in that it comprises a polyvinylidene fluoride resin porous body 'and an inorganic filler dispersed in the porous body. The "polyvinylidene fluoride resin" used in the present invention is a thermoplastic fluororesin. It is printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs and contains at least 50% by weight, preferably at least 75% by weight of vinylidene fluoride. As a resin structural unit. Therefore, it is not limited to a homopolymer including only vinylidene fluoride, and may be a copolymer of vinylidene fluoride and one or more monomers selected from the following monomers. Copolymerizable monomers For example, tetrafluoroethylene, trifluoroethylene, trifluoroethylene, gaseous ethylene, hexafluoropropylene, acetamidine, and perfluoroalkyl ethers are preferred as the polyvinylidene fluoride copolymer. Copolymer of vinylidene fluoride and hexafluoropropylene (Do not include hexafluoropropylene content _ -5- National paper standard applicable to this paper size) ~~ · ~ A7 B7 Five 'invention description (3) more than 15 weight %). This thermoplastic polyvinylidene fluoride resin can be obtained by emulsion polymerization method, suspension polymerization method and other commonly used polymerization methods, and the melt flow rate (MFR) is preferably from 0.05 to 1 〇. 〇g / 10 minutes (at 23 ° C and 2-16 kg load Measured below), more preferably from 〇〇〇 to 20 grams 80 minutes. In the present invention, 'per 100 parts by weight: polyvinylidene fluoride resin should be added 2 to 200 parts by weight, more preferably 5 to 5 0 parts by weight of inorganic fillers. The inorganic fillers used in the present invention can be used in many kinds of high polymer materials (Reference ,, The Dictionary of Filler Application [Fira Katsuyo Jiten] ", Fira Kenkyukai Edit, Taiseisha Issue '1 994). In particular, inorganic oxides and silicates are preferably used. Examples of inorganic oxides are silicon dioxide, aluminum oxide, diatomaceous earth' titanium oxide, calcium oxide, zinc oxide, Magnesium oxide, tin oxide, ferrite, and the like. Among these, the use of alumina and silica produced by the decomposition method is particularly good. Furthermore, examples of the silicate are calcium silicate, talc , Mica, montmorillonite, bentonite, sepiolite, .imogolite, sericite 'glass fiber and glass beads, etc. The shape of the inorganic filler is not particularly limited, and it may be fibrous, needle-like, Platelet or granular. Member of the Ministry of Economic Affairs, Central Bureau of Commerce, Consumer Cooperation, Yinfan (please read the precautions on the back before filling out this page). Furthermore, the surface of the aforementioned inorganic filler can be obtained by functional groups with hydroxyl groups on the surface (such as silanol! )), Which reacts with silicon compounds (such as silicon halides, oxysilanes, silazane, siloxanes, and the like) and is hydrophobic. The method for producing a battery separator of the present invention is not particularly limited A known method for producing a porous body from a high polymer resin can be used. As a conventional method, there is a method called a sol-gel method, which uses a solution of a high polymer resin and a non-solvent. To be clear, the aforementioned inorganic fillers are dispersed in _ '6-Consumer Cooperation of Central Standards Bureau of the Ministry of Economic Affairs, printed 424347 A7 ______B7 V. Description of the invention (4) The polyvinylidene fluoride resin is dissolved in a solvent The obtained solution was then obtained by contacting this solution with a non-solvent of polyvinylidene resin to obtain a porous body. In this case, N-methyl-pyrrolidone, formamidine, dimethylamidamine 'dimethylacetamidamine, diamidine are used as solvents for the purpose of dissolving poly (vinylidene fluoride). Obstruction, r-butyrolactone, tetramethylene gland, trimethyl vinegar, propionate, fluorenyl ethyl ketone, tetrahydrofuran and the like. Moreover, their mixtures can also be used as a bulking agent. The concentration of the polyvinylidene fluoride resin contained in the solution is normally from 5 to 50% by weight, preferably from 10 to 30% by weight. As the poor solvent, water or alcohol is preferably used, and water is particularly preferred. By contacting a polyvinylidene fluoride resin solution (the preparation of which is described above) containing a dispersed inorganic filler with a poor solvent, the sol-gel conversion starts immediately, and a porous body is produced. In this case, the contact should preferably be carried out for a long period of time with an insoluble solvent to extract the solvent from the porous body, which is a poor solvent containing a small amount of a solvent that depolymerizes the vinylidene fluoride resin. This—contact time will vary depending on the size of the porous body, but is usually preferably at least 0 seconds, more preferably at least 30 seconds. The desired porous body shape of the battery separator is a film. The thickness is preferably from 5 to 200 microns, and more preferably from 10 to 100 microns. The pore diameter is preferably not more than 20 µm ', more preferably from 0.05 to 0 µm. In terms of porosity, 5 to 85% is better and 5 to 80% is better. The porous body of the present invention can also (if necessary) be stretched (hot stretched or cold stretched) or touched with some treatment, or both, to increase the crystallinity or fix the crystal structure. The draw ratio will vary depending on the type of resin (molecular weight and comonomer content), the manufacturing conditions of the porous body, etc., but it will be appropriately from K1 to _ -7. This paper size applies the Chinese national standard CNS) Λ4 specifications (2 丨 0 \ 297 male_ ^ ~] ---------— (Please read the precautions on the back before filling in this page) Install '、 Ya
4 2 4 3 r- 第87109667號專利申請案 說明書修正頁(89年6月） 五、發明説明（5 ) 6，但低於斷裂拉伸比，較佳為從12到4。拉伸可以是單 向或雙向（同時或連續）。推荐的熱理溫度是從7〇至155 t，較佳10〇至150t。熱處理可以自由狀態或在控制之收 縮下’以固定長度或伸展狀態進行，但使用伸展狀態時伸 展百分比理想地將不超過1〇%，較佳不超過5%。簡言 之此較佳在一疋範圍内，如此，在熔體固化時形成之球 粒才致破碎，而在破碎與轉換成細結晶前之狀態發生成 長。 可藉由暴露於高能量（通常2至4〇兆拉德（megarad))電子 束或T射、.泉’或藉由化學去氫氟（dehydr〇flU〇rinati〇n)反 應，將交聯引進本發明的多孔體中。用此法，可提高多孔 禮的耐熱性和機械強度。4 2 4 3 r- Patent application No. 87109667 Correction page of the specification (June 1989) 5. Description of the invention (5) 6 but lower than the elongation at break, preferably from 12 to 4. Stretching can be unidirectional or bidirectional (simultaneous or continuous). The recommended thermal temperature is from 70 to 155 t, preferably from 100 to 150 t. The heat treatment can be performed in a free state or under a controlled shrinkage 'at a fixed length or in an extended state, but when using the extended state, the percentage of extension will ideally not exceed 10%, preferably not exceed 5%. In short, this is preferably within a range, so that the pellets formed when the melt solidifies are broken, and the state before the crushing and conversion into fine crystals grows. Crosslinking can be performed by exposure to high-energy (usually 2 to 40 megarad) electron beams or T-rays, .springs, or by chemical dehydrofluorine (dehydrflfl 〇rinatin) reaction. Introduced into the porous body of the present invention. In this way, the heat resistance and mechanical strength of the porous body can be improved.
經濟部中央標準局員工消費合作社印U 以下將解釋以上述方式所得多孔膜在鋰電池的應用。明 確"T之，使用一個陽極，其係由一層陽極活性材質在集電 極之至少一面形成所製成；—個陰極，其係由—層陰極活 性材質在集電極之至少一面形成所製成；和前述多孔膜， 此多孔膜即放在陽極和陰極之間，以致彼等不接觸，且這 些不是層合，就是捲成一捲（螺旋狀）的形式，然後放入適 當的容器内。在此容器内加入電解質溶液，其係由至少一 種選自 LiPF6、LiBF4、CiCl〇4、LiAsF6、LiN(CF3S02)2、 LiCF3S〇3和LiSbF0等的趣鹽’溶解於一適當溶劑中（主要是 碳酸酯’如碳酸伸乙酯、碳酸伸丙酯或碳酸二甲酯等），然 後將容器密封後’最後就得到電池，換言之，本發明多孔 體的使用狀態是多孔區域充滿了前述的電 -8- 本纸張尺度適用中國國家標率（CNS ) A4規格（210χ 297公鸾；） 严 A7 B7 五、發明説明（6 ) 解質溶液’同時包含聚偏二氣乙晞樹脂的多孔膜的基質區 域則呈被電解質溶液泡脹的狀態。 ' —在此’作:電極的集電極’可以使用金屬、金屬網或 二維多孔體幸，但較佳爲’集電極所用的金屬應爲不备與 鐘輕易形成合金的金屬。特定言之，鐵、鎳、姑、 鋁、鈦、釩、鉻和錳本身或合金都可使用。 π極活性材貝中’負電極活性材質應該是可以進行 和未摻雜㈣子的材質。此種材質的實例爲焦炭材質^ 石油基或碳基炭焦(coke)等、乙決黑或其他此種碳黑、石 土玻璃貝竣、，古性破、碳纖維和含唆物質，如藉由在非 氧化氛圍中燃燒有機高聚合物所得的燒過錢聚合物。甚 至’也可加入氧化銅。 作爲^電極活性材質可以使用過渡金屬氧化物如二氧化 1孟和五氧化二M，過渡金屬氧化物（原文如此）如硫化鐵和 硫化鈇，和這些與錢的複合化合物（例b :㈣複合氧化 物、鋰姑鎳複合氧化物和鋰錳氧化物)和類似物。當將此稀 物質併合於正電極時，係將—種溶劑與藉由將適當的電導 體(碳是最常用的)與黏結劑加至粉狀正電極活性物質的混 合物混合’以製造糊狀物’然後將其騎於集電極上並乾 燥，<後視情況進行壓結，即得電極。 [實例] 以下將藉一些實例來更明確地解釋本發明，但是本發明 並不是僅限制於這些實例。 [實例1 ] 9- 私紙狀度適财賴家料（CNS ) Αιί規格（2mx297公楚 ί請先聞讀背面之注意事項再填寫本頁} 裝 -訂-- 結濟部中央榡準局員工消費合作社印製 A7 A7 經濟部中央插準局員工消費合作社印製 五、發明説明（7 ) ~~一' 將15重量份的Kynar 741(由ELF Atochem製造的聚偏二 氟乙烯樹脂；MFR値〇.3克/1 〇分[在23CTC及2.16 kg負荷 下測得])溶解於8 5重量份的N ·甲基吡咯烷酮。將4重量 份的非結晶狀氧化矽（大部份粒子大小爲2 〇 n m )，（由四 氣化矽和氫終熱分解方法所得）分散於此溶液中，繼之，將 此混合物鑄造到聚對苯二甲酸乙二醇酯支撐膜上，並浸在 水中2小時，即得5 0微米厚度的多孔膜。此膜的氧化矽含 量是2 1重量％。此膜有約4 〇 %的孔隙性和在内部有多數 近1微米的孔洞。 將此膜浸在電解質溶液中〗小時，此溶液係得自濃度爲 1M的LiPF6 ’落解於碳酸伸乙酯（EC)和碳酸伸丙酯（pc) 1 1 : 1混合物中，之後使用普通電橋測量它的導電度。得 到的値約是比較實例1之値的3倍。當此已用電解質溶液 泡脹的膜加熱至6 0 °C時，發現此膜形狀仍很穩定未破裂a [實例2 ] 使用經過球磨機研磨過的煤瀝青焦炭，作爲負極活性物 質支撐物，將其1 00重量份加至！ 0重量份聚偏二氟乙烯 (由 ELF Atochem 製造的 Kynar 301F : MFR 0.03 克/10 分在 230 C及2.1 6 kg負荷下）溶於N_甲基吡咯烷酮，作爲黏結 劑所形成之溶液中，即形成泥漿（糊狀物）。將此泥漿旋塗 在厚度2 0微米之銅箔的兩面，在i 2〇。匸下留置！小時後， 即進行減壓乾燥和壓結，而得厚度14〇微米和寬度2〇厘米 的負電極。 接著，以下列方式而得正電極。將1 〇〇重量份Lic〇〇2作 -10- 本紙伕尺度適用中國國家標準規格（210X297公潑） * ： ---------裝------訂 (請先M讀背面之注意事項再填寫本頁) A7 B7 經濟部中央榇华局員工消費合作社印製 五、發明説明（8 爲正兒極居性材質’及6重量份石墨作爲電導劑，分散於 含有 重量备聚偏二氟乙晞（ICynar 3 1 OF)作爲黏結劑之， 甲基吡咯烷酮中’以產生泥漿（糊狀物）。將此泥槳施塗於 厚度2 0微米的鋁箔的兩面，並在12〇 下留置I小時後， 即進行減壓乾燥和壓結，而得厚度16〇微米和寬度2〇厘米 的正電極。 使用如此所得負和正電極，和實例1所得多孔膜作爲隔 板’將這些依隔板、負電極、隔板、正電極和隔板的順序 分別重疊一起，之後將此層合物捲成螺旋形式，即得螺旋 狀见極sa。接著，在連接導線到電極體上的相對電極之 後’將其放人不銹鋼容器中，再將1MLipF6溶解於凌酸伸 ㈣和U2-二甲氧乙燒之同體積混合物中的溶液，作爲電 解質，倒入容器中。 在充電/放電試驗中，充電起始是進行至4」v，電流密 度爲30心每丨克碳’然後，用同樣的方式，放電係在同 樣電流下進行至2.5V。第二次，和之後，在同樣條件下 重校无電和放電，並根據放電能量進行電池之評估。牡 果，第_週期的放電能量非常優異，至少是第]〇週㈣ 6 0%。 [實例3 ] 以與實炉"同樣的方式製備多孔膜，除了不用― 74卜而用Ky则，其係偏二氟乙缔和 製造U氟丙烯’（六氟丙埽含量約1〇重量％，戲仿 0.2 克 10 分[在 230 X：及 2.16 kg έ 苻下 μ " g貞何r所測量])的共聚合 一 -11 - 本纸張尺度適用中國國家標準（CNS ) A4規格（210X 297公楚） (請先閲讀背面之注意事項再填《;"本頁) 裝 ------ I.—訂--Γ ---- 4^4347 A 7 B7 五、發明説明（9 物’且不用氧切而用細顆粒的^ .氧化IS »此膜中的氧化 ，含量馬2 1重量％。膜的孔隙性爲约3 〇 %且在内部有許 夕近1微米的孔洞3再者’當用與實你"同樣方式測量電 導度時，所得之値爲比較實例2之約3倍。 [比較實例1] 將由15重量份Kynar 741溶於85重量份N_甲基吡咯烷 酮所得之溶液’鏵造到對笨二曱酸乙二醇醋支搏膜上，然 後浸在水中2小時，即得厚度5G微米的多孔膜。此膜的孔 隙性爲40%且在内部有許多近i微米的孔洞。 *將此膜浸在電解質溶液中；!個小時，該電解質係由濃度 爲1M LiPFe浴于碳酸伸乙酯（E c)和碳酸伸丙酯（p c)之 1 : 1混合物中而得。隨後，用普通電橋測量其導電度，得 到 0.3 ms/cm。 [比較實例2 ] 用與比較實例！同樣的方法製備多孔膜，除了不用比較 實例1中所用的Kynar 741，而用Kynar28〇i。此膜的孔 隙性爲約30%且在其内部有許多近丄微米的孔洞。再者， 用比較實例1同樣的方式測量導電度時，得到〇 4 ms/cm。 [本發明的效應] 如以上所解釋，本發明的電池隔板擁有 ，其 製備容易且其具有突出的機械特性。當用作爲經電池隔板 時’由於聚偏二II乙烯是阻燃性’故所形成的爲比使用聚 乙烯隔板更安全的電池。 -12- 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公楚）Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs, the following will explain the application of the porous membrane obtained in the above manner in lithium batteries. To be clear " T, an anode is used which is made of a layer of anode active material formed on at least one side of the collector; a cathode is made of-a layer of cathode active material is formed on at least one side of the collector And the aforementioned porous membrane, which is placed between the anode and the cathode so that they are not in contact with each other, and these are either laminated or rolled into a roll (spiral) form, and then placed in a suitable container. An electrolyte solution is added to the container, which is dissolved in at least one interesting salt selected from LiPF6, LiBF4, CiCl04, LiAsF6, LiN (CF3S02) 2, LiCF3S〇3, LiSbF0, etc. Carbonate esters such as ethyl carbonate, propylene carbonate, or dimethyl carbonate, etc.), and then the container is sealed, and finally the battery is obtained. In other words, the porous body of the present invention is used in a state in which the porous region is filled with the aforementioned electricity- 8- This paper scale applies Chinese National Standard (CNS) A4 specifications (210x297 mm); Yan A7 B7 V. Description of the invention (6) Degradation solution 'Porous membrane containing PVDF resin The matrix area is in a state of being swollen by the electrolyte solution. '-Here' as the "collector of the electrode", a metal, a metal mesh, or a two-dimensional porous body can be used. Fortunately, the metal used for the 'collector should be a metal that is not easily alloyed with a bell. In particular, iron, nickel, aluminum, aluminum, titanium, vanadium, chromium, and manganese may be used per se or alloys. The active material of the negative electrode of the π-pole active material should be a material that can be used and undoped with raccoon. Examples of such materials are coke materials ^ petroleum-based or carbon-based carbon coke, etc., ethylene black or other such carbon black, stone earth glass shell, archaic, carbon fiber and thorium-containing substances, such as borrow Burned polymer obtained by burning organic high polymers in a non-oxidizing atmosphere. It may even be added with copper oxide. As the electrode active material, transition metal oxides such as 1 MgO and 2M pentoxide, transition metal oxides (the original text) such as iron sulfide and thorium sulfide, and these compound compounds with money (example b: rhenium compound) can be used. Oxides, lithium nickel complex oxides, and lithium manganese oxides) and the like. When this dilute substance is incorporated into the positive electrode, a solvent is mixed with a mixture of powdery positive electrode active material by adding an appropriate electric conductor (carbon is most commonly used) and a binder to the paste to produce a paste. The object is then mounted on the collector electrode and dried, and the back electrode is pressed as necessary to obtain an electrode. [Examples] The present invention will be explained more clearly with some examples, but the present invention is not limited to these examples. [Example 1] 9- Private Paper Applicability (CNS) Αιί Specifications (2mx297 Gongchu) Please read the notes on the back before filling out this page} Binding-Bookmarking-Central Government Bureau of Economic Affairs Printed by employees' consumer cooperatives A7 A7 Printed by the Central Consumer Bureau of the Ministry of Economic Affairs Employees' cooperatives V. Description of invention (7) ~~ 1 '15 parts by weight of Kynar 741 (Polyvinylidene fluoride resin manufactured by ELF Atochem; MFR 0.30 g / 10 minutes [measured at 23CTC and 2.16 kg load]) dissolved in 85 parts by weight of N · methylpyrrolidone. 4 parts by weight of amorphous silica (most particle size 20nm), (obtained by the method of final pyrolysis of silicon tetrahydrogen and hydrogen) were dispersed in this solution, and then the mixture was cast onto a polyethylene terephthalate support film and immersed in After 2 hours in water, a 50-micron-thick porous film was obtained. The silicon oxide content of the film was 21% by weight. The film had a porosity of about 40% and most of the pores of nearly 1 micron inside. This film Immersed in an electrolyte solution for hours, this solution was obtained from LiPF6 'at a concentration of 1M C) and propylene carbonate (pc) 1 1: 1 mixture, and then measured its conductivity using an ordinary bridge. The obtained 値 is about 3 times the 比较 of Comparative Example 1. When this has been swelled with the electrolyte solution When the film was heated to 60 ° C, it was found that the shape of the film was still stable and unbroken. [Example 2] Coal pitch coke ground with a ball mill was used as a negative electrode active material support, and 100 parts by weight was added to it! 0 parts by weight of polyvinylidene fluoride (Kynar 301F manufactured by ELF Atochem: MFR 0.03 g / 10 min at 230 C and 2.16 kg load) is dissolved in N-methylpyrrolidone, as a solution formed as a binder, A slurry (paste) is formed. This slurry is spin-coated on both sides of a copper foil with a thickness of 20 microns, and left under i 2 0. ！! After hours, it is dried under reduced pressure and pressed to obtain a thickness of 14 Negative electrode with a width of 20 micrometers and a width of 20 cm. Next, a positive electrode was obtained in the following manner. 1000 parts by weight of Lic002 was used as -10- The standard of this paper is in accordance with Chinese national standard specifications (210X297). --------- Install ------ Order (Please read the precautions on the back before filling (Write this page) A7 B7 Printed by the Consumers' Cooperative of the Central Ronghua Bureau of the Ministry of Economic Affairs. 5. Description of the invention As a binder, thallium (ICynar 3 1 OF) is used in methylpyrrolidone to produce a slurry (paste). This mud pad is applied to both sides of an aluminum foil having a thickness of 20 μm and left at 120 ° C for 1 hour. After that, drying and pressing under reduced pressure were performed to obtain a positive electrode having a thickness of 160 μm and a width of 20 cm. Using the thus obtained negative and positive electrodes, and the porous membrane obtained in Example 1 as separators, these were laminated together in the order of the separator, the negative electrode, the separator, the positive electrode, and the separator, and then the laminate was rolled into a spiral form. , That is, the spiral shape see pole sa. Next, after connecting the wire to the opposite electrode on the electrode body, 'put it into a stainless steel container, and then dissolve 1MLipF6 in a solution of the same volume mixture of lindonic acid and U2-dimethoxyethane, as the electrolyte, Pour into a container. In the charge / discharge test, the charge start was performed to 4 "v and the current density was 30 cores per gram of carbon '. Then, in the same manner, the discharge was performed to 2.5V at the same current. The second time, and after, recalibrate the dead and discharge under the same conditions, and evaluate the battery based on the discharge energy. In fact, the discharge energy of the first cycle is very good, at least 60% of the first week. [Example 3] A porous membrane was prepared in the same manner as in a real furnace, except that Ky was used instead of "74", which is based on difluoroethylene and Ufluoropropylene '(hexafluoropropane content of about 10 weight %, Parody 0.2 g 10 points [measured at 230 X: and 2.16 kg μ μ " gzhenhe r]) copolymerization -11-This paper size applies Chinese National Standard (CNS) A4 specifications (210X 297 Gongchu) (Please read the precautions on the back before filling "" this page." -------- I.—Order--Γ ---- 4 ^ 4347 A 7 B7 V. Invention Note (9 things' and fine particles without oxygen cutting. Oxidation IS »Oxidation in this film, the content is 21.1% by weight. The porosity of the film is about 30% and there is almost 1 micron in the interior. Holes 3 and "when the conductivity is measured in the same manner as the real one", the resulting mass is about 3 times that of Comparative Example 2. [Comparative Example 1] 15 parts by weight of Kynar 741 is dissolved in 85 parts by weight of N_ The solution obtained from methylpyrrolidone was made into a p-aqueous dimer acid acetic acid membrane and then immersed in water for 2 hours to obtain a porous film with a thickness of 5G microns. The porosity of this film was 40% and there are many pores of nearly i micrometers inside. * This membrane is immersed in an electrolyte solution; for hours, the electrolyte is made of a 1M LiPFe bath in ethylene carbonate (Ec) and propylene carbonate (Pc) in a 1: 1 mixture. Subsequently, the conductivity was measured with an ordinary bridge to obtain 0.3 ms / cm. [Comparative Example 2] A porous membrane was prepared in the same manner as in Comparative Example, except that no Comparative Example was used. Kynar 741 was used in 1, and Kynar 28〇i was used. The porosity of this film was about 30% and there were many pores of approximately 丄 m inside. Furthermore, when the conductivity was measured in the same manner as in Comparative Example 1, it was obtained 〇4 ms / cm. [Effect of the present invention] As explained above, the battery separator of the present invention possesses that it is easy to prepare and has outstanding mechanical characteristics. When used as a battery separator, it is due to the polyisocyanate II Ethylene is flame retardant, so it is a battery that is safer than using polyethylene separators. -12- This paper size applies to China National Standard (CNS) A4 specification (210X297)
In HI 1 --r--^--裝-- (請先閱讀背面之ii·意事項再填寫本頁) 經濟部中央標準局—工消費合作社印製In HI 1 --r-^-install-(Please read the ii and notice on the back before filling out this page) Printed by the Central Standards Bureau of the Ministry of Economic Affairs—Industrial and Consumer Cooperatives