200405602 玖、發明說明： … m (」二_ )發明所屬之枝術領域： . 本發明係關於製造隔板之方法，特別係關於使用於鋰離 子電池中之隔板，及關於所製造之隔板本身及配置該隔板 之電池。 電隔板是使用於電池及其他設備中（其中必須將電極相 互分離，同時例如維持離子導電率）之隔板。 隔板通常是一種薄而多孔之絕緣材料，其具有離子高滲 0 透性、良好機械強度和對於該系統中所使用之化學藥劑和 溶劑，例如，電池中之電解質而具有長期穩定性。電池中 ，隔板應將陰極與陽極完全電絕緣而使電解質能通過。且 ，該隔板必須具有永久彈性並遵循系統中之移動，例如， 在充電和放電的過程中之電極組合。 隔板對於使用隔板在其中之設備的使用壽命，例如電池 組的使用壽命，具有極重要之決定因素。因此，可再充電 電池領域之發展，端賴適當隔板材料之開發進度。 β 關於電隔板和電池之一般資訊例如可在0. Besenhard 之π雷池材料手冊"（VCH-Verlag, We i n h e i m，1 9 9 9 )中見到。 目前使用之隔板主要係由多孔有機聚合膜或無機非織物 (例如，是由玻璃或陶瓷材料要不然陶瓷紙所組成之非織物） 所組成。此等係由不同公司所製造的。重要製造廠商包括 Celgard、Tonen、Ube、Asahi(旭化成）、Binzei.、三菱、Daramic 及其他。典型有機隔板，例如係由聚丙烯或聚丙烯/聚乙燃/ 200405602 聚丙烯之複合材料所組成。 此等有機聚烯烴隔板的缺點是其顯然低於1 5 〇 t;之相當 低之熱安定性界限，以及其在無機鋰電池組中之低的化學 安定性。當使用於鋰電池中作爲隔板時，聚烯烴由鋰或鋰 化之石墨逐漸侵蝕。在包含聚合物電解質之系統中，於是 形成了稠密的氧化產物層，其可防止更進一步的破壞鋰離子 電池中之隔板。 (二）先前技術 : 初期曾經有試圖使用無機複合物材料作爲隔板。例如， 德國專利1 9 8 3 8 8 0 〇號包括一種電隔板，其包含具有許多 開孔並具有一塗層在該基板上之片狀撓性基板，該隔板之 特徵爲基板的材料係選自金屬、合金、塑膠、玻璃、碳纖 維或其組合，而該塗層是一片二維式連續多孔不導電之陶 瓷塗層。然而’經測定此等隔板（如所例示，其係由導電材 料予以承載）並不適合於鋰離子電池，因爲在所述之厚度時 該隔板不能大面積地製造而無缺點，而因此可能極易發生 短路現象。 槪括地說明’目前沒有供製造捲繞式高性能或高能量電 池之適當的隔板材料，尤其在以經濟的方式製造。 德國專利1 9 9 1 8 8 5 6號中記述採用聚合纖維的基板（施 加聚合物和陶瓷之混合物至其上）之非水性電解質電池隔 板’唯陶瓷分率極小。此等隔板可在至多高達1 2 〇 °C下使 用，因爲超過此溫度導致離子導電率之中斷。 在先前操作（德國1 0 1 4 2 6 2 2 )中，吾等能證明可能獲得 200405602 含有片狀撓性基板之一種材料’該基板具有許多開孔並具 有一塗層在此基板上及其中，而基板的材料係選自玻璃或 陶瓷或其組合之織物或非織物之不導電纖維，而該塗層是 多孔、電絕緣陶瓷塗層，所產生之隔板具有小於1 ΟΟμιη (微米）之厚度且係可彎曲的，具有連通至電解質時之充分 低電阻，且尙能具有充分良好之長期穩定性。但是就許多 應用而言，此等隔板的電阻仍太高，因爲所使用之基板是 織物之玻璃纖維織物，第一係因此基板太厚；第二係因具 有不充分之孔隙。 在德國專利1 〇 1 4 2 6 2 2中所述之進行隔板性質的最適化 過程中’出人意外地發現，具有上述性質之隔板可由使用 聚合基板材料而獲得。此方式提供之電隔板，具有許多開 孔且其具有一塗層在此基板上及在其中之片狀撓性基板， 該基板的材料係選自聚合物的非織物不導電纖維，而該塗 層係多孔電絕緣之陶瓷塗層。該隔板具有小於3 5 μ 1Ώ之厚 度且可彎、曲’且連通至電解質時具有充分低電阻，另外具 有充分長期穩定性。此等隔板的熱安定性於具多孔無機塗 層的熱安定性。雖然如尙未公告之德國專利案1〇2 〇8 2 77 5虎中所述之此等隔板，係極適用於所述之工作，但是余等 確定其中所述之方法會產生高比例的碎屑，因爲關於其中 所述之隔板’極難相當大量地製造，例如，在特別作爲 大面積下（至少5 0厘米）其不具有裂縫、摺疊和孔隙的網 片0 冬 200405602 明內容： 因此，本發明的一個目的在提供一種方法’其可大量製 造〜種電隔板，包含具有許多開孔及一個多孔無機塗層在 該板上及其中之片狀撓性基板，該基板的材料係選自聚合 纖維所選出之非織物不導電纖維，且宜具有超過5 0 %的孔 隙度，在至少5 0厘米的網片寬度中並無裂縫、摺疊和孔 隙。 現已出人意料地發現，在塗覆操作期間此類隔板可經由 不超過最大牽引張力（關於特定聚合物需測此張力）以大容 積製成而無缺點。出人意料以外，余等亦發現：可以加工 處理比甚至較德國專利1 〇 1 4 2 6 2 2中所述網片更細的材 料。 現已確定在塗覆操作期間，遵守1 ΟΝ/cm的最大張力及 低於所使用之聚合物的軟化溫度，至少2 (TC之最大溫度是 避免所製造之隔板而有任何破裂、撕裂、彎曲、摺疊或變 形之一種方式，而藉以減少拒收率而至極顯著程度，即拒 收率低於1 0 %，而較佳爲低於5 %。 因此’本發明提供連續製造隔板之方法，該隔板含有 許多開孔’其有一多孔無機電絕緣塗層在基板上及在其中 之片狀撓性基板，基板的材料係選自非織物不導電之聚合 物纖維而基板具有超過5 0 %之孔隙度，此方法包括將基板 自一個輥上展開，透過塗覆操作（其中提供塗層在基板上） 及將預先製造之隔板捲繞在第二輥上，其特徵爲使該基板 在塗覆操作期間，經縱方向之1 〇 N / c m的最大張力受力及 魯 200405602 在該塗覆操作期間作熱處理。 本發明另外提供一種由本發明方法所製造之隔板。 本發明更另外提供一種含有根據本發明之隔板的電池。 本發明的方法利於製造隔板，符合本發明目的之隔板係 爲電之隔板，例如，其爲將互相分離兩種不同電荷之電極 。又該隔板，其電池需要一種電解質，能使離子自一個電 極通過該隔板而至另一個電極。該電解質係根據電池所使 用之化學系統而予以選擇。 就大體而論，隔板中之孔隙愈大，當將孔隙充滿適當電 解質時，伴隨發生之電阻愈低。而且，隔板的孔隙度可透 過選擇適當的粒子而加以改變，而此方式相似導致性質之 改良。關於這一點經常所引用之一個隔板參數是Gurley數 値，其是一種乾的多孔隔板的透氣性之量度。如由〇 · Besenhard在電池材料手冊中所述，所知系統的導電率可 自GurUy數値直接推斷。以一般化之術語而言，較高之透 氣性（即：較小之Gurley數値）可獲得電池組中潤濕下隔板 的較高導電率。商業上所供應之隔板的G u r 1 e y數値範圍， 自1 〇 (此時孔隙直徑約〇 ·1 μm )至3 0 (此時孔隙直徑約爲 0·05μ m )(G. Veil ugio fa 1; J. of Power Sources 77(1999) 31-41)° 然而，必須經常牢記在心的是極小的G u r 1 e y數値亦可能 是隔板缺陷的跡相（例如孔隙大）°此等缺陷可導致電池操 作時發生內部短路。因此該電池在可能反應極快地自行放 電下而發生危險。在該程序中’在極端情況下而發生大電 -11- 200405602 池，其甚至於造成所包含之電池組爆炸。因此之 對於鋰高能電池是否具安全性、或缺少安全性而 性作用。因此，隔板是電池的一個關鍵性結構組 値得注意。 聚合物隔板提供了，例如，目前鋰電池所需要 能，其可藉由超出停工溫度（其是大約12 〇 °c )時， 極間任何離子輸送來達成，這是因爲，在此溫度 的孔隙結構會陷縮及所有孔隙會閉合。由於停止 的結果，所以中止了可導致爆炸之危險反應。然 由於外部之環境，使電池組更進一步地加熱，則超》 之崩潰溫度。在此溫度下，隔板開始熔化和收縮 電極在電池組中之許多位置上造成直接接觸，有 內部短部。此現象導致了失控反應，其最後仍是 組爆炸，或將所產生之壓力，經由洩壓閥（爆裂ί ，其經常具有著火的痕跡。 本發明的隔板是一種混成隔板，因爲其包含了 和一種聚合物系之基本材料，因此，使用本發明 板，由於高溫，當基本材料聚合物之結構熔化並 機材料的孔隙中藉以將孔隙閉合時而發生停工。 用本發明之隔板不致發生熔化。憑藉其電池組中 構，本發明之隔板因而符合各種電池製造商所期 全地關閉電流之機構的要求。無機粒子保證該隔 能熔化，因此也保證絕不可能發生大面積之短路 如果爲了實際上的應用，絕對必須附加關閉電 故，隔板 具有決定 件且非常 之安全性 可阻礙電 下，隔板 離子輸送 而，如果 i 約 1 6 5 °c 。然後兩 大面積之 形成電池 I )而釋放 無機組份 之混成隔 滲透入無 然而，使 之停工機 望之可安 板絕不可 〇 流之機構 200405602 ，則此附加之關閉電流機構，例如亦可將本發明的陶瓷或 混成隔板的表面及/或孔隙，另配以一種材料而予以完成， 當達到溫度極限時，此材料將堵塞孔隙而防止離子之繼續 流動。例如，此可藉一種聚合物或鱲（其熔點是在該範圍內） 而予以達成。 設若’例如，由於偶發事件所發生內部短路，本發明的 隔板亦極安全。舉例而言，如果一個釘子刺穿電池，因爲 隔板的型式，下列情況就可能發生聚合之隔板在刺穿之位 置可能熔化（短路電流流經釘子而使它升溫）並收縮，其結 果是短路位置可能變得愈來愈大，而反應可能失控。然而 本發明的混成隔板中，僅聚合之基板材料可能被熔化（如果 全然被熔化），惟無機隔板材料部份仍不熔化。因此，接續 此偶發事件後’電池組內部中之反應可能更爲溫和地進行 。因此，此電池較具有聚合隔板之電池顯然較爲安全，尤 其是應用在車輛中，這是一個重要因素。 本發明的混成隔板之另外一個値得考量的優點是，其具 極爲良好的潤濕性。對於親水性陶瓷塗層，使用一般電解 層，例如碳酸伸乙基酯（E C )、碳酸伸丙基酯（p c )和碳酸二 甲酯（DMC)作爲潤濕，可極速地進行。然而，在較少親水 性電解質的情況中，亦可使表面特別具有疏水性。此乃意 指：電池是敏銳的而因此使用此隔板亦能製造經濟性。 本發明的隔板較具體而言，例如德國專利i 〇丨42 622中 所述之織造玻璃或陶瓷織物爲基材之隔板具有明顯的成本 利益。除去大部份不同的材料成本以外，此明顯的成本利 200405602 益之一個原因’即是聚合基板較織造玻璃或陶瓷織物大體 在處理上較爲簡單，畢竟，織造玻璃或陶瓷織物具有相當 的脆性且不小心處理會造成損壞。因此整個製造操作較不 便利因此是成本密集。 然而’現已確定是在先前技藝方法中不能使用聚合纖維 基板用以製造隔板’先前技藝方法利用的是玻璃纖維或金 屬纖維基板。在某些實例中，問題爲，特別是需要使用高 達2 8 0 °c溫度而未固化陶瓷組份。特別是，陶瓷和聚合物 的熱膨脹係數之差別太大而是一個困難的問題。另外，聚合 物在此等較高溫度下接觸，而藉以進行一定程度的收縮。 而且’以聚合纖維爲基材之基板，在筒溫度和所施加之牽 引張力的雙重條件下，經常會變得拉伸。由於此等影響之 結果’藉由習用機器參數所製成之隔板，經常在縱方向會 具有波狀起伏。在某些事例中，與使用作爲基板之原料比 較，此等波狀起伏或摺疊，致使隔板的寬度彎窄而高達5 0% 或甚至7 0 %。再者，當捲繞預先製成之隔板時，隔板中之 波狀起伏經常可導致皺摺及/或折疊，而因此在材料中形成 破裂和孔隙以致不再可能使用，此供其實際目的之用的材 料必須作爲拒收處理或破片材料而拋棄。另外一個問題即 在冷卻過程中，塗層自基板上分離，因爲在冷卻操作中塗 層材料收縮率小於基板材料而因此易於脫離。 但是現已發現出人意外地，如果遵守特定機器參數，可 將塗層仍然施予適合於製造玻璃或金屬織物爲基材之隔膜 之機器上，特別是如果在塗覆操作期間，使該基板在縱方 -14- 200405602 向歷經小於1 0 N / c m之最大張力。爲了遵守機器參數，特 佳例係修正該方法，其經由採用輔助裝置，即所謂之拉幅 機’塗覆操作期間選擇溫度’以便經常保持低於聚合物的 軟化溫度之下2 (TC。 現在將敘述本發明的方法，及本發明的隔板，而本發明 並非受於此限。 本發明方法係用於連續地製造隔板，此隔板包含具有許 多開孔’在該基板上及在其中具有一多孔無機電絕緣塗層 之片狀撓性基板’該基板的材料係選自非織物不導電之聚 合纖維’而該基板具有超過5 0 %之孔隙度；此方法包括將 基板自一個輥上展開，並透過塗覆操作（在此操作中使基板 具有塗層），而將預先製成之隔板捲繞在第二輥上；其特徵 爲使基板在塗覆操作期間，在縱方向承受1 ON/cm的最大 張力，及在塗覆操作期間進行熱處理。 基板的材料，係選自非織物聚合纖維。舉例而言，非織 物聚合纖維可能是形成線圈狀之針織物、非織物或毛氆。 特別合宜的是，該撓性基板是由聚合纖維所組成或含有聚 合纖維之非織物。使用的非織物較佳爲極薄而均勻之網片 材料，在連通至電解質之應用中，可提供均勻的電阻。非 織物，相對於織物，具有顯然較大孔隙度的優點。 所使用之基板的孔隙度，自50%至9 7 %範圍內，更宜自 5 0 %至9 0 %範圍內，而最宜自6 0 %至9 0 %範圍內。關於這 一點，孔隙度之定義爲非織物的體積（1 〇〇%)減去非織物 200405602 纖維之體積’亦即，未被材料所佔據之非織造物體積之分 率。非織物的體積，可自非織物的因次予以計算。設定爲 問題之纖維體積’係非織物所量測的重量及聚合纖維的密 度予以計算。基板的大孔隙度亦意指本發明的混成隔板具 有較大孔隙度’此係爲何使用本發明之隔板可吸收較高的 電解質。 基板的材料，特佳地以選自纖維厚度〇 · 1至1 Q μΐΏ之聚合 纖維的非織物。本發明的隔板，包括厚度5至3 0 μ m (而宜 10至20 μηι)之基板可能特別有利。基板的厚度對於隔板的 性質具有實質上影響，因爲不僅撓性而且電阻受電解質飽 和之隔板的薄片，係依賴於基板的厚度。另外，較薄之隔 板可使電池堆中增加較多塡充密度，以便可將較大的能量 儲存在相等體積中。爲了能獲得具有絕緣性質之隔板，所 使用之基板宜包括聚合物的不導電纖維，其宜選自聚丙腈 (PAN)、聚酯，例如聚對苯二甲酸乙二酯（pet)及/或聚烯烴 (PO)、舉例而言例如聚丙烯（PP)或聚乙烯（PE)或此等聚烯 烴的混合物。所有其他聚合物使用在電池之極具反應性的 介質中係同樣地穩定之，但是上述之化合物係爲特佳之材 料。所使用之基板，宜包括具有超過1 〇(TC之軟化溫度和 超過11 0 °C之熔化溫度的聚合纖維。聚合纖維的直徑是〇 . ! 至1 0 μ m (而宜1至5 μ m )可能有利。 塗層宜由施加至基板上及其中，其係藉由包含宜係A 1 、Ζι*及/或Si等元素的至少一種不導電或僅極不良導電氧 化物及一種溶膠的懸浮液，並加熱一或數次以固化，在基 -16- 200405602 板上及在其中之5亥懸浮液。該方法本身，可自世界專利w ， 9 9/ 1 5 2 6 2得知，但是並非用以製造本發明的隔板所有的參 數和原料，特別是不導電原料均可使用。開始原料的選擇 亦支配首先必須找出之某些程序參數，以便有用材料的組 合，以作爲隔板。 懸浮液，舉例而言，可由印刷在其上、壓製在其上、壓 入其中、輥壓在其上、刮刀塗佈至其上、覆蓋塗覆至其上 '浸漬、噴灑或傾倒在其上而被帶至基板上及至其中。 使用於製備塗層之懸浮液包括Zr、Α1及/或Ai等元素或 馨 其混合物的至少一種溶膠’且係由懸浮至少一種無機組份 在至少一種的此等溶膠中而予以製備。經由懸浮作爲無機 組份之自Zr、A1和Si等元素的氧化物所選出之至少一種 氧化物於溶膠中，以製備懸浮液係可能有利。所懸浮之組 份的質量分率宜是所使用之溶膠者1至2 5 0倍，更宜1至 5 〇倍。所懸浮之組份宜具有2 0至1 0 0 0 0奈米的平均粒子 大小或基本粒子之5至1 〇 〇 〇 〇奈米的平均大小。 溶膠係藉由使用水或一種酸或其組合以水解上述元素中 ® 的至少一種化合物所獲得。在溶液水解前，將欲予水解之 化合物引入一種醇或一種酸或此等液體的組合中係可能同 樣有利。欲予水解之化合物宜是至少一種之硝酸鹽、鹵化 物、氯化物、碳酸鹽或烷醇鹽化合物。所水解之烷醇鹽化 合物宜是Zr、A1及/或Si等元素的烷醇鹽化合物。該水解 宜在液體水、水蒸汽、冰或一種酸或其組合的存在下進行。 -17- 200405602 f四）奮施方式= 本發明方法的一個具體實施例，包括經由將欲予水解之 化合物水解而製得顆粒溶膠。此等顆粒溶膠，經由水解戶斤 形成之化合物，係以顆粒形式存在呈現爲於溶膠而値得注 意。此顆粒溶膠可如上所述或如世界專利（WO) 9 9/ 1 5 2 6 2中 所述而予以製備。此等溶膠通常具有極高含水量，其宜高 於5 0重量％。在溶液水解前，將欲予水解之化合物引入醇 或酸或其組合中可能有利。可將經過水解之化合物經由至 少一種有機或無機酸處理予以解膠，宜使用10-60%有機或 無機酸，特別宜使用選自硫酸、氫氯酸、過氯酸、磷酸、 硝酸或其混合物之一種無機酸。而隨後使用如此製成之顆 粒溶膠來製備懸浮液，在此情況中，最好製備供應用在預 處理過之聚合型溶膠之聚合纖維非織物的懸浮液。 在本發明方法的另一具體實施例中，將欲予水解之化合 物水解來以應用於製備聚合溶膠。在本發明方法的此較佳 具體貫施例中’該溶膠具有少於5 0重量％的水及/或酸分 率。此#聚合丨谷膠因下列事實値得注意即：經由水解所形 成之化合物係以聚合形式’即以越過相當大空間予以交聯 之鏈的形式而存在於溶膠中。此等聚溶膠通常包括少於5 〇 重量％的水及/或含水酸，而宜遠少於20重量％。爲了獲得 水及/或含水酸的較佳分率，水解宜以例如一種方式進行， 以便將欲予水解之化合物使用於可水解化合物爲基質的可 水解基團’以0.5至10倍莫耳比（而宜使用一半莫耳比）的 液體水、水蒸汽或冰予以水解。在水解非常慢之化合物， -18- 200405602 例如四乙氧基矽烷的情況中，所使用之水量可能高達1〇 倍。水解極快速之化合物，例如四乙醇銷在此等條件下完 全可以形成顆粒溶膠，這是爲何最好使用〇 · 5倍的水量， 以水解此等化合物。使用少於較佳數量的液體水、水蒸汽 或冰來水解亦同樣可獲良好結果，唯使用超過5 0%或少於 較佳數量的一半之該莫耳比亦屬可能，但不是非常可明顯 ，因爲使用低於此一數量水解可能不再完全，此等溶膠爲 基材之塗層可能極不安定。 爲了製備此等溶膠，在進行實際水解前，將欲予水解之 化合物溶入一種有機溶劑中可能有利，有機溶劑特別是乙 醇、異丙醇、丁醇、戊醇、己烷、環己烷、乙酸乙酯及/ 或其混合物，可使用如此製備之溶膠來製備本發明之懸浮 液。 可使用顆粒狀溶膠及聚合溶膠兩者以作爲一種溶膠來製 備本發明方法中之懸浮液。並非僅可使用如上所述而獲得 之溶膠，而是原則上亦可使用商業上所供應之溶膠，例如 硝酸锆溶膠或矽溶膠。經由施加懸浮液至載體上並將它在 載體上固化來製造隔板的方法，自德國專利1 0 1 42 622號 及自WO 9 9/ 1 5 2 62相似形式，就其本身而論係爲熟知，但 是並非所有參數和成分都可應用於製備本發明之隔膜。更 特定而言’ WO 9 9/ 1 5 2 62中所述之操作並非以此形式完全 可應用於聚合之非織物材料。 爲了改進無機組份於聚合纖維基板之黏著性，將所使用 之懸浮液與黏著促進劑混合，例如有機官能矽烷係可能有 ^19- 200405602 利。有效之黏著促進劑，特別包括選自下列之化合物，辛 基砂垸 '乙烯基矽烷、胺官能化之矽烷及/或縮水甘油基官 能化之矽烷，例如來自Degussa公司之Dynasilanes。適合 聚乙烯（PE)和聚丙烯（PP)之特佳黏著促進劑是乙烯基、甲 基和辛基等矽烷’唯獨特使用甲基矽烷並不最適宜；適合 聚醯胺和多元胺’其爲胺官能化之矽烷；適合聚丙烯酸酯 和聚酯’其爲縮水甘油基官能化之矽烷而適合聚丙烯腈， 亦可能爲使用縮水甘油基官能化之矽烷。同樣可使用其他 之黏著促進劑’但是彼等必須適應於各自之聚合物。因此 ’必須選擇黏著促進劑，以便使其固化溫度低於使用作爲 基板之聚合物的熔化或軟化溫度，並低於其分解溫度。根 據本發明之懸浮液，宜包括明顯少於2 5重量％，而更宜少 於1 0重量％的能充作黏著促進劑之化合物。黏著促進劑的 最適宜分率，係由使用單分子層的黏著促進劑塗覆纖維及/ 或粒子而獲得。爲了此目的所需要之黏著促進劑之數量 (以克計），可經由將所使用之氧化物或纖維的數量（以克計） ’乘以材料的比表面積（以計），然後除以黏著促進劑 所需要之特定面積（以n^g·1計）而獲得，所需要之特定面積 經常係自3 0 0至4 0 0 m2 g-1的數量級。 下列表1爲一覽表，其含有關於典型的非織物材料聚合 物，有機官能矽化合物爲基材之可使用的黏著促進劑。 -20- 200405602 表1200405602 (ii) Description of the invention:… m ("二 _)" Field of invention:. The present invention relates to a method for manufacturing separators, in particular to separators used in lithium ion batteries, and to the separators manufactured The board itself and the battery with the separator. Electrical separators are separators used in batteries and other equipment where the electrodes must be separated from each other while maintaining, for example, ionic conductivity. The separator is usually a thin and porous insulating material with high ionic permeability, good mechanical strength, and long-term stability to chemicals and solvents used in the system, such as electrolytes in batteries. In a battery, the separator should completely insulate the cathode from the anode so that the electrolyte can pass through. And, the separator must have permanent elasticity and follow the movement in the system, for example, the combination of electrodes during charging and discharging. The separator is a very important determinant of the service life of the equipment in which the separator is used, such as the battery life. Therefore, the development of the field of rechargeable batteries depends on the development progress of appropriate separator materials. β General information about electrical separators and batteries can be found, for example, in the π Thunder Cell Material Handbook of 0. Besenhard (VCH-Verlag, We i n h e i m, 199 9 9). The separators currently used are mainly composed of porous organic polymer membranes or inorganic non-woven fabrics (for example, non-woven fabrics composed of glass or ceramic materials or ceramic paper). These are manufactured by different companies. Key manufacturers include Celgard, Tonen, Ube, Asahi (Asahi Kasei), Binzei., Mitsubishi, Daramic and others. Typical organic separators are, for example, composed of polypropylene or polypropylene / polyethylene / 200405602 polypropylene composite materials. The disadvantages of these organic polyolefin separators are that they are clearly lower than 150 ° C; rather low thermal stability margins, and their low chemical stability in inorganic lithium battery packs. When used in lithium batteries as separators, polyolefins are gradually eroded by lithium or lithiated graphite. In a system containing a polymer electrolyte, a dense oxidation product layer is formed, which prevents further damage to the separator in the lithium ion battery. (II) Prior technology: At first, there were attempts to use inorganic composite materials as separators. For example, German Patent No. 1 988 8 800 includes an electrical separator including a sheet-shaped flexible substrate having a plurality of openings and a coating on the substrate. The separator is characterized by the material of the substrate. It is selected from metal, alloy, plastic, glass, carbon fiber or a combination thereof, and the coating is a two-dimensional continuous porous non-conductive ceramic coating. However, it has been determined that these separators (as illustrated, which are carried by a conductive material) are not suitable for lithium-ion batteries, because the separator cannot be manufactured in a large area without defects at the stated thickness, so it may be Extremely prone to short circuit. In a nutshell, there are currently no suitable separator materials for the manufacture of wound high-performance or high-energy batteries, especially in an economical manner. German Patent No. 1 9 1 8 8 5 6 describes that a non-aqueous electrolyte battery separator 'using a polymer fiber substrate (to which a mixture of polymer and ceramic is applied) is provided with a very small ceramic fraction. These separators can be used at temperatures up to 120 ° C, as exceeding this temperature results in interruption of ionic conductivity. In previous operations (Germany 1 0 1 4 2 6 2 2), we can prove that it is possible to obtain 200,405,602 a material containing a sheet-like flexible substrate 'the substrate has many openings and has a coating on this substrate and in it The material of the substrate is a non-conductive fiber selected from glass or ceramics or a combination of woven or non-woven fabrics, and the coating is a porous, electrically insulating ceramic coating. The resulting separator has a thickness of less than 100 μm (microns). Thick and flexible, has a sufficiently low resistance when connected to the electrolyte, and has sufficient long-term stability. However, for many applications, the resistance of these separators is still too high, because the substrate used is woven glass fiber fabric. The first system is therefore too thick; the second system has insufficient porosity. In the process of optimizing the properties of the separator described in German Patent No. 104 2 622, it was unexpectedly discovered that a separator having the above properties can be obtained by using a polymer substrate material. The electrical separator provided in this manner has a plurality of openings and has a sheet-shaped flexible substrate coated on and in the substrate. The material of the substrate is selected from the group of non-woven non-conductive fibers of polymer, and the The coating is a ceramic coating of porous electrical insulation. The separator has a thickness of less than 3 5 μ 1Ώ, is bendable, curved, and has sufficiently low resistance when connected to an electrolyte, and has sufficient long-term stability. The thermal stability of these separators is due to the thermal stability of porous inorganic coatings. Although these partitions, as described in the unpublished German Patent Case No. 102 0 2 77 5 Tiger, are extremely suitable for the work described, it remains to be determined that the methods described therein will produce a high proportion of Debris, as it is extremely difficult to manufacture relatively large quantities with regard to the partitions described therein, for example, meshes that do not have cracks, folds, and voids especially in large areas (at least 50 cm). Therefore, it is an object of the present invention to provide a method 'which can produce a large number of kinds of electrical separators, including a sheet-shaped flexible substrate having a plurality of openings and a porous inorganic coating on the plate and the substrate, and the material of the substrate It is selected from non-woven non-conductive fibers selected from polymeric fibers, and preferably has a porosity of more than 50%, without cracks, folds and voids in a mesh width of at least 50 cm. It has now surprisingly been found that such separators can be made in large volumes without disadvantages during the coating operation by not exceeding the maximum traction tension, which is measured for specific polymers. Surprisingly, Yu et al. Also found that it is possible to process materials that are finer than the meshes described in German Patent 101 4 2 6 2 2. It has been determined that during the coating operation, a maximum tension of 100N / cm is observed and the softening temperature of the polymer used is at least 2 (the maximum temperature of TC is to avoid any cracking or tearing of the manufactured separator) , Bending, folding, or deforming, and thereby reducing the rejection rate to a significant degree, that is, the rejection rate is less than 10%, and preferably less than 5%. Therefore, the present invention provides a continuous manufacturing of separators. Method, the separator contains many openings, which has a porous inorganic electrical insulating coating on the substrate and a sheet-shaped flexible substrate therein, the material of the substrate is selected from non-woven non-conductive polymer fibers and the substrate has more than 5 0% porosity, this method includes unrolling a substrate from a roller, through a coating operation (where a coating is provided on the substrate) and winding a pre-manufactured separator on a second roller, characterized in that the During the coating operation, the substrate is subjected to a maximum tensile force of 10 N / cm in the longitudinal direction and the heat treatment is performed during the coating operation. The present invention further provides a separator manufactured by the method of the present invention. Furthermore, a battery containing a separator according to the present invention is provided. The method of the present invention facilitates the manufacture of the separator. The separator that meets the purpose of the present invention is an electrical separator, for example, it is an electrode that separates two different charges from each other. The battery of the separator requires an electrolyte that can pass ions from one electrode through the separator to the other electrode. The electrolyte is selected based on the chemical system used in the battery. Generally speaking, in the separator, The larger the pores, the lower the electrical resistance that occurs when the pores are filled with the proper electrolyte. Moreover, the porosity of the separator can be changed by selecting the appropriate particles, and this approach similarly results in improved properties. Often this is the case One of the separator parameters cited is the Gurley number, which is a measure of the permeability of a dry porous separator. As described in the Battery Materials Handbook by Besenhard, the conductivity of the known system can be calculated from the GurUy number. Directly inferred. In general terms, a higher permeability (ie, a smaller Gurley number) can obtain a lower wetted separator in the battery pack. Electrical conductivity. The G ur 1 ey number range of commercially available separators ranges from 10 (in this case, the pore diameter is about 0.1 μm) to 30 (in this case, the pore diameter is about 0.05 μm) (G Veil ugio fa 1; J. of Power Sources 77 (1999) 31-41) ° However, it is important to keep in mind that very small G ur 1 ey numbers may also be traces of separator defects (such as large pores). ° These defects can cause an internal short circuit when the battery is operating. Therefore, the battery is dangerous when it may respond to self-discharge extremely quickly. In this procedure, a large electricity occurs in an extreme case-11- 200405602 battery, which even Causes the contained battery pack to explode. Therefore, it has an effect on the safety or lack of safety of lithium high-energy batteries. Therefore, the separator is a key structural group of batteries. The polymer separator provides, for example, the energy required by current lithium batteries, which can be achieved by any ion transport between the poles above the shutdown temperature (which is about 120 ° C), because, at this temperature, The pore structure will collapse and all pores will close. As a result of the halt, the dangerous reaction that could lead to an explosion was suspended. However, due to the external environment, the battery pack is further heated, exceeding the collapse temperature. At this temperature, the separator begins to melt and shrink. The electrodes make direct contact at many locations in the battery pack, with internal shorts. This phenomenon leads to an out-of-control reaction, which in the end is still an explosion of the group, or the pressure generated is passed through a pressure relief valve (burst ί), which often has traces of fire. The separator of the present invention is a hybrid separator because it contains Because of the high temperature, the use of the board of the present invention, due to the high temperature, when the structure of the base material polymer melts and the pores of the organic material are closed to stop the pores. Using the separator of the present invention does not cause Melting occurs. By virtue of the structure of the battery pack, the separator of the present invention therefore meets the requirements of various battery manufacturers for a mechanism that shuts off the current completely. Inorganic particles ensure that the separator can melt, so it is also impossible to cause large-area If the short circuit is necessary for practical application, it is absolutely necessary to turn off the power. The separator has a decisive component and the safety is very high. It can hinder the ion transport of the separator. If i is about 16 5 ° c. Form the battery I) and release the mixture of inorganic components to infiltrate. However, make the shutdown machine safe and secure. 200405602, then this additional current-closing mechanism can also be completed by, for example, the surface and / or pores of the ceramic or hybrid separator of the present invention with another material. When the temperature limit is reached, this material will block the pores and Prevent the flow of ions. This can be achieved, for example, by a polymer or rhenium whose melting point is within this range. Suppose, for example, that the separator of the present invention is also extremely safe due to an internal short circuit due to an incident. For example, if a nail pierces the battery, because of the type of separator, the following may happen. The polymerized separator may melt (the short-circuit current flows through the nail and heats it up) at the pierced position and shrinks. The result is The position of the short circuit may become larger and larger, and the reaction may be out of control. However, in the hybrid separator of the present invention, only the polymerized substrate material may be melted (if completely melted), but the inorganic separator material portion is still not melted. Therefore, after this incident, the reaction inside the battery pack may proceed more gently. Therefore, this battery is obviously safer than batteries with polymer separators, especially in vehicles, which is an important factor. Another advantage considered in the hybrid separator of the present invention is that it has extremely good wettability. For hydrophilic ceramic coatings, the use of general electrolytic layers such as ethylene carbonate (EC), propyl carbonate (pc), and dimethyl carbonate (DMC) as wetting can be performed very quickly. However, in the case of less hydrophilic electrolytes, the surface can also be made particularly hydrophobic. This means that the battery is sharp and therefore the use of this separator can also be made economically. More specifically, the separator of the present invention, for example, a woven glass or ceramic fabric-based separator described in German Patent No. 42 622 has a significant cost benefit. Except for most of the different material costs, one obvious reason for this obvious cost benefit is 200405602. That is, the polymeric substrate is generally simpler to handle than woven glass or ceramic fabric. After all, woven glass or ceramic fabric is quite brittle And careless handling will cause damage. The entire manufacturing operation is therefore less convenient and therefore cost intensive. However, 'it has been determined that polymer fiber substrates cannot be used to make separators in the prior art method' Prior art methods used glass fiber or metal fiber substrates. In some instances, the problem is, in particular, the need to use uncured ceramic components at temperatures up to 280 ° C. In particular, the difference between the coefficients of thermal expansion of ceramics and polymers is too large but a difficult problem. In addition, the polymer is contacted at these higher temperatures, thereby shrinking to some extent. Furthermore, a substrate made of polymer fibers often becomes stretched under the dual conditions of the barrel temperature and the traction tension applied. As a result of these effects, the separator made of conventional machine parameters often has undulations in the longitudinal direction. In some cases, these undulations or folds cause the width of the separator to be narrowed by as much as 50% or even 70% compared to the use of raw materials as substrates. Furthermore, when a pre-made separator is wound, the undulating waves in the separator can often cause wrinkles and / or folds, and thus cracks and voids are formed in the material so that it is no longer possible to use it. The materials used for the purpose must be discarded as rejects or fragments. Another problem is that the coating is separated from the substrate during the cooling process, because the coating material shrinks less during the cooling operation than the substrate material and is therefore easily detached. However, it has now been found that, surprisingly, if certain machine parameters are adhered to, the coating can still be applied to a machine suitable for making glass or metal fabric-based separators, especially if the substrate is made during a coating operation In the vertical direction -14- 200405602, it experienced a maximum tension of less than 10 N / cm. In order to comply with machine parameters, a particularly preferred method is to modify the method by using an auxiliary device, a so-called tenter 'selection temperature during coating operation' in order to constantly keep it below the softening temperature of the polymer 2 (TC. Now The method of the present invention and the separator of the present invention will be described, and the present invention is not limited thereto. The method of the present invention is used for continuously manufacturing a separator including a plurality of openings on the substrate and on the substrate. A sheet-shaped flexible substrate having a porous inorganic electrical insulating coating 'the material of the substrate is selected from non-woven non-conductive polymer fibers' and the substrate has a porosity of more than 50%; the method includes A roll is unrolled, and a pre-made separator is wound on a second roll through a coating operation (in which the substrate is coated), which is characterized in that the substrate is Withstand a maximum tension of 1 ON / cm in the longitudinal direction and heat treatment during the coating operation. The material of the substrate is selected from non-woven polymer fibers. For example, non-woven polymer fibers may form a coil shape Knitted fabric, non-woven fabric, or fleece. Particularly suitable is that the flexible substrate is a non-woven fabric composed of or containing polymeric fibers. The non-woven fabric used is preferably an extremely thin and uniform mesh material. In the application of electrolyte, it can provide uniform resistance. Non-woven fabrics have the advantage of significantly larger porosity compared to fabrics. The porosity of the substrate used ranges from 50% to 97%, more preferably from 5% 0% to 90%, and most preferably 60% to 90%. In this regard, porosity is defined as the volume of the nonwoven (100%) minus the volume of the nonwoven 200405602 fibers 'That is, the fraction of the volume of the nonwoven that is not occupied by the material. The volume of the nonwoven can be calculated from the dimensions of the nonwoven. The fiber volume set as the problem' is the weight and polymerization measured by the nonwoven The density of the fiber is calculated. The large porosity of the substrate also means that the hybrid separator of the present invention has a larger porosity. This is why the separator of the present invention can absorb higher electrolytes. The material of the substrate is particularly preferably Selected from fiber thickness · Non-woven fabrics of 1 to 1 Q μ 纤维 of polymer fibers. The separator of the present invention may include substrates having a thickness of 5 to 30 μm (preferably 10 to 20 μηι). The thickness of the substrate has properties for the properties of the separator. It has a substantial effect, because not only the flexibility but also the resistance of the electrolyte-saturated separator depends on the thickness of the substrate. In addition, thinner separators can increase the charge density in the battery stack so that larger The energy is stored in equal volumes. In order to obtain a separator with insulating properties, the substrate used should include polymer non-conductive fibers, which is preferably selected from polyacrylonitrile (PAN), polyester, such as polyterephthalic acid Ethylene glycol (pet) and / or polyolefin (PO), for example polypropylene (PP) or polyethylene (PE) or a mixture of these polyolefins. All other polymers are equally stable in the highly reactive medium of the battery, but the compounds mentioned above are particularly good materials. The substrate used should include polymer fibers having a softening temperature exceeding 10 ° C and a melting temperature exceeding 110 ° C. The diameter of the polymer fibers is from 0.1 to 10 μm (and preferably from 1 to 5 μm ) May be advantageous. The coating should preferably be applied to and into the substrate by suspending at least one non-conductive or only very poorly conductive oxide and a sol containing at least one element such as A 1, Z * and / or Si. Liquid, and heated one or several times to cure, the suspension on the base-16-200405602 plate and in it. The method itself can be known from the world patent w, 9 9/1 5 2 6 2 but Not all parameters and raw materials used to make the separator of the present invention, especially non-conductive materials, can be used. The choice of starting materials also governs certain program parameters that must be found first so that the combination of useful materials can be used as the separator Suspensions, for example, can be printed on, pressed onto, pressed into, rolled onto, coated with a doctor blade, coated onto it by 'dipping, spraying or pouring on it On the substrate and into it. Used in preparation The coating suspension comprises at least one sol 'of elements such as Zr, A1 and / or Ai or a mixture thereof and is prepared by suspending at least one inorganic component in at least one of these sols. The suspension is used as the inorganic group It may be advantageous to prepare at least one oxide selected from oxides of elements such as Zr, A1, and Si in a sol to prepare a suspension system. The mass fraction of the suspended component should be 1 to 1 250 times, more preferably 1 to 500 times. The suspended component should preferably have an average particle size of 20 to 100 nm or an average size of 5 to 1000 nm of the basic particles. Sol is obtained by using water or an acid or a combination thereof to hydrolyze at least one compound of the above-mentioned elements. Before the solution is hydrolyzed, the compound to be hydrolyzed is introduced into an alcohol or an acid or a combination of these liquids May be equally advantageous. The compound to be hydrolyzed is preferably at least one nitrate, halide, chloride, carbonate or alkoxide compound. The hydrolyzed alkoxide compound is preferably an element such as Zr, A1 and / or Si Alkanol Compound. The hydrolysis is preferably carried out in the presence of liquid water, water vapor, ice or an acid or a combination thereof. -17- 200405602 f) Fent application mode = a specific embodiment of the method of the present invention, including The compound is hydrolyzed to prepare a granular sol. These granular sols, which are formed by hydrolyzing household compounds, are in the form of particles and appear as sols. This particulate sol can be prepared as described above or as described in World Patent (WO) 9 9/1 5 2 6 2. These sols usually have a very high water content, which is preferably higher than 50% by weight. Prior to solution hydrolysis, it may be advantageous to introduce the compound to be hydrolyzed into an alcohol or acid or a combination thereof. The hydrolyzed compound can be degummed by treatment with at least one organic or inorganic acid, preferably 10-60% organic or inorganic acid, particularly preferably selected from sulfuric acid, hydrochloric acid, perchloric acid, phosphoric acid, nitric acid or mixtures thereof An inorganic acid. Then, the granule sol thus prepared is used to prepare a suspension. In this case, it is preferable to prepare a suspension of a polymer fiber non-woven fabric for use in a pretreated polymer sol. In another embodiment of the method of the present invention, the compound to be hydrolyzed is hydrolyzed to be used for preparing a polymeric sol. In this preferred embodiment of the method of the present invention, the sol has a water and / or acid fraction of less than 50% by weight. This #polymer 丨 glutin is noticed due to the fact that the compound formed by hydrolysis exists in the sol in a polymerized form, that is, in the form of a chain that is crosslinked across a considerable space. These polysols generally include less than 50% by weight of water and / or aqueous acids, and preferably much less than 20% by weight. In order to obtain a better fraction of water and / or water-containing acid, the hydrolysis is preferably carried out, for example, in a manner such that the compound to be hydrolyzed is used for the hydrolyzable group of the hydrolyzable compound as a matrix, with a molar ratio of 0.5 to 10 times (Although half Morse ratio should be used) liquid water, steam or ice to hydrolyze. In the case of very slow hydrolysis compounds, such as -18-200405602, such as tetraethoxysilane, the amount of water used may be as much as 10 times. Compounds that hydrolyze very quickly, such as tetraethanol pin, can completely form granular sols under these conditions, which is why it is best to use 0.5 times the amount of water to hydrolyze these compounds. Hydrolysis using less than a better amount of liquid water, steam or ice can also yield good results, but it is also possible to use more than 50% or less than half of the better amount, but it is not very feasible Obviously, because the hydrolysis may not be complete with less than this amount, the coating of these sol-based substrates may be extremely unstable. In order to prepare these sols, it may be advantageous to dissolve the compound to be hydrolyzed in an organic solvent before the actual hydrolysis, especially organic solvents such as ethanol, isopropanol, butanol, pentanol, hexane, cyclohexane, Ethyl acetate and / or mixtures thereof can be used to prepare the suspensions of the present invention using the sols thus prepared. Both granular sols and polymeric sols can be used as a sol to prepare a suspension in the method of the present invention. It is not only possible to use the sols obtained as described above, but in principle it is also possible to use commercially available sols, such as zirconium nitrate sols or silica sols. A method for manufacturing a separator by applying a suspension to a carrier and curing it on the carrier, from German Patent No. 1 0 1 42 622 and similar forms from WO 9 9/1 5 2 62, as far as it is concerned is It is well known, but not all parameters and ingredients can be applied to make the separator of the present invention. More specifically, the operations described in ' WO 9 9/1 5 2 62 are not fully applicable in this form to polymeric non-woven materials. In order to improve the adhesion of the inorganic component to the polymer fiber substrate, the suspension used is mixed with an adhesion promoter. For example, organic functional silanes may be beneficial. Effective adhesion promoters include, in particular, compounds selected from the group consisting of octyl succinates, vinyl silanes, amine-functionalized silanes and / or glycidyl functional silanes, such as Dynasilanes from Degussa. The best adhesion promoters suitable for polyethylene (PE) and polypropylene (PP) are silanes such as vinyl, methyl, and octyl. The unique use of methyl silane is not the most suitable; suitable for polyamines and polyamines. It is an amine-functional silane; suitable for polyacrylates and polyesters. It is a glycidyl-functional silane and suitable for polyacrylonitrile. It may also be a glycidyl-functional silane. Other adhesion promoters' can be used as well but they must be adapted to their respective polymers. Therefore, the adhesion promoter must be selected so that its curing temperature is lower than the melting or softening temperature of the polymer used as the substrate, and lower than its decomposition temperature. The suspension according to the present invention preferably includes significantly less than 25% by weight, and more preferably less than 10% by weight of a compound capable of acting as an adhesion promoter. The optimum fraction of the adhesion promoter is obtained by coating the fibers and / or particles with an adhesion promoter of a single molecular layer. The amount of adhesion promoter (in grams) needed for this purpose can be obtained by multiplying the amount of oxides or fibers (in grams) by the specific surface area of the material (in grams) and dividing by the adhesion The specific area required by the accelerator (in n ^ g · 1) is obtained, and the specific area required is often in the order of 300 to 400 m2 g-1. Table 1 below is a list containing typical adhesion promoters for typical non-woven polymer materials and organic functional silicon compounds as substrates. -20- 200405602 Table 1
聚合物 有機官能型式 黏著促進劑 PAN 縮水甘油基 GL ΥΜΟ 甲基丙烯醯氧基 MEMO PA 胺基 AMEO、DAMO PET 甲基丙烯醯氧基 MEMO 乙烯基 VTMO、 VTEO、 VTMOEO ΡΕ,ΡΡ 胺基 AMEO、ΑΜΜΟ 乙烯基 VTMO、VTE〇、Silfin 甲基丙烯醯氧基 MEMO 其中：Polymer organic functional type adhesion promoter PAN glycidyl GL ΥΜΟ methacryl methoxy MEMO PA amino AMEO, DAMO PET methacryl methoxy MEMO vinyl VTMO, VTEO, VTMOEO PE, PP amino AMEO, AMU Vinyl VTMO, VTE〇, Silfin methacryloxy MEMO where:
AMEO = 3-胺（基）丙基三乙氧基矽烷 DAMO = 2-胺（基）乙基-3-胺（基）丙基三甲氧基矽烷 GLYM 0 = 3-縮水甘油氧基三甲氧基矽烷 MEMO = 3-甲基丙烯醯氧基丙基三甲氧基矽烷 Silfin=乙烯基矽烷+引發劑+觸媒 VTEO =乙烯基三乙氧基矽烷 VTMO =乙烯基三甲氧基矽烷 VTMOEO =乙烯基三（2-甲氧基乙氧基）矽烷 根據本發明方法的特別具體實施例中，在先前步驟中， 係將上述之黏著促進劑施加至基板上，特別是施加至聚合 之非織物上。因此之故，將黏著促進劑溶入一種適當溶劑 中，例如乙醇。此溶液可另外包括少量的水（宜〇. 5至1〇 倍莫耳數量的可水解之基團）及少量的一種酸，例如H C 1 -21- 200405602 或Η Ν Ο 3作爲水解及縮合s i - 0 R基團用之觸媒。將此溶液 藉由熟悉技術施加至基板上，例如，噴灑在其上、印刷在 其上、壓製在其上、壓入其中、輥壓在其上、刮刀塗佈在 其上、覆蓋塗佈在其上、浸漬、噴灑或傾倒在其上，而該 黏著促進劑係由5 0至不超過3 5 0 t下之熱處理而予以固定 在基板上。僅在施加黏著促進劑後，根據本發明方法的此 具體實施例，具有經施加並固化之懸浮液。 在實際施加懸浮液前，施加黏著促進劑可提供改良黏著 性的基板，特別關於水性顆粒溶膠，這是爲何根據本發明 特別可將如此預處理之基板，可使用商業級可供應之溶膠 ’例如硝酸銷溶膠或矽溶膠之懸浮液以進行塗覆。但是此 種施加黏著促進劑的方式，亦意指根據本發明隔膜之製造 程序’必須擴展包括插進或初步處理步驟。雖然其較使用 已添加黏著促進劑至其中之可用溶膠昂貴，而且不便，但 此方式仍可實行，亦具有優點，即爲於使用商業級可供應 溶膠之懸浮液時，可獲得較佳結果。 根據本發明之塗層，係藉由固化在基板中及在其上之懸 浮液。根據本發明’存在於基板上及其中之懸浮液可加熱 至5 0〜3 5 0 °C下而予以固化。因爲當使用聚合基板材料時 ’最大溫度受所使用之基板所支配，因此必須適應最大溫 度。因此’根據本發明方法的具體實施例而言，將存在於 基板上和其中之懸浮液，加熱至1 〇 〇〜3 5 0 °C下而固化，最 宜加熱至1 1 0〜2 8 0 °C。加熱至1 〇 〇〜3 5 0 °C下，且歷1秒至 6 〇分鐘可能有利。更宜加熱至1 1 〇〜3 〇 〇它下以來固化懸浮 -22 - 200405602 液，最宜加熱至11 0〜2 8 0 °c，且宜歷〇 · 5至〗〇分鐘，即 熱處理，特別是在低於聚合物材料的軟化溫度至少2 〇 t之 溫度下來進行。 按照所選擇之溫度範圍來固化隔板，某些聚合物材料在 熱影響下可能造成其化學結構之改變，以致此等聚合物隨 後不再以其原來狀悲、或變體而存在。例如，聚醯亞胺可能 部份碳化，而聚丙烯腈可能形成所謂的梯形聚合物，其隨 後歷經部份碳化。此等影響性經常可導致載體材料的性質 之改變。 根據本發明’可藉由加熱之空氣、熱氣、紅外線輻射或 經由根據先前技藝之其他加熱方法之組合予以加熱。 根據本發明之連續程序’宜由下列之操作予以進行，將 基板自一個輥上展開，以lm/h至2m/s之速率下（宜自 〇.5ni/min 至 2 0m/min 之速率，最宜自 lm/min 至 5m/niin 之 速率）’使其通過至少一個裝置（例如一只輥），其施加懸浮 液於載體頂上及入其中，及通過至少另外一個裝置，其將 懸浮液經由加熱，例如使用一具電熱爐，而在載體上及其 中固化’並在第二輥上捲繞如此製成之隔板。此操作能以 連續地程序製造根據本發明之隔板。相同地，經由遵守所 述之參數，可在連續基礎而進行預處理程序。 如前所述’該程序必須以如此方式進行，以便在塗覆操 作或各操作期間’尤其在熱處理（乾燥）期間，基板具有在 縱方向lON/cm的最大張力，宜不超過3N/Cm，最宜不超過 0.1 N/cm。關於這一點，術語”塗覆操作”係述及所有處理步 -23- 200405602 驟，其中將材料帶至基板上及入其中，並經由熱處理在其 上予以固化◦在塗覆操作期間，宜將基板以0.001至3N/cm 的最大力予以拉伸。在塗覆操作或各操作期間，基板在縱 方向實際上未予拉伸可能係特別合宜。 爲了可能不致發生載體材料的變形，甚至彈性變形，必 須極精確控制牽引張力。由於過度大的牽引張力可能變形 (伸展），其可能意指陶瓷塗層不能遵循構造之材料，結果 是塗層可變得與基板材料整個大面積地分離。因此所產生 之產物不能滿足所意欲之目的而被使用。若不注意到上述 具有多孔陶瓷之聚合基板材料之塗覆限制顯然不可行。 爲了控制或設定張力，經確定爲在塗覆操作期間，導引 基板至至少兩輥筒或輥上係有利。宜將（各）輥或輥筒配以 一個驅動器’且關於該兩輥或輥筒，其旋轉速率宜分開且 可控制。另外之輥可存在於此兩輥或輥筒之間。額外之輥 不一定須予以驅動，但可成爲純粹支持輥之構型，其可極 易旋轉於輥或輥筒。但是使此等之輥，每一皆具有其本身 驅動’可分開，可控制且亦可能有利。 可將各輥以如此方式配置，以便該基板垂直、水平或相 對於重力以任何其他所需要之角度而移動。該基板最好以 垂直或水平移動。兩方向具有其優點和缺點。當基板在施 加和倂合塗覆材料的過程中及在材料隨後固化的過程中之 垂直移動時’基板不可能在兩輥之間下垂，因此在施加塗 覆材料期間承受不受控制之伸展。因爲其本身的重量，須 避免材料的任何縱向拉伸，假若在垂直導引之時，絕對必 -24- 200405602 須特別在施加塗覆材料後，將基板導引至使其離開固化設 · 備（通常是烘箱）的位置。 現已確定關於所欲進行之本發明程序，特別有利的是’ 在塗覆操作期間，且特別是在熱處理期間應維持基板在拉 幅機中，使用拉幅機保證基板由於其本身重量而不會過度 張緊。爲了此目的，拉幅機具有側向之導承，在塗覆操作 期間所以支持基板。拉幅機中之導引，亦保護在熱處理的 過程中發生之網片的任何正常收縮，將獨特地反映在網片 的厚度中，而非在材料之立向因次中。該拉幅機更宜具有 側向導承，其具有移動輔助設備，且宜配置一個可調整之 驅動器。該移動輔助設備，宜嚙合至基板中或將它夾緊， 並可以選擇其速率而移動。 此種拉幅機之一種可能的具體實施例，係由兩個被驅動 輥筒或輥所組成速率可予以調整。此等輥筒之間，有以輥 筒的速率進行之鏈或帶，其在輥的一或兩端上。將此等鏈 或帶以正常間隔配置，且能嚙合至基板中之輔助設備。此 類輔助設備，舉例而言可能是（短）鞘、夾或能嚙合至基板 中之相似設備。爲了輔助設備在基板上可具有充分支點， 現已確定使輔助設備在距基板網片的邊緣〇 · 2至2厘米之 距離，嚙合至基板中係有利。爲了獲得均勻分佈的力，現 已測定使輔助設備嚙合在基板的各面上，使呈均勻分佈係 特別有利。此現象可經由輔助設備之連續或以均勻間隔嚙 合在基板中而予以實現，該等間隔範圍爲〇(連續）至1 5厘 米，而宜爲1至10厘米。 -25 - 200405602 在較佳變體中，在捲繞隔板前，將由於拉幅機所形成且 不能使用於電池中之缺陷邊緣區域，直接地連續切除。此 操作宜由固定或旋轉刀片進行。由於切割陶瓷隔板而使刀 片快速鈍化，而不能再利落切割隔板，刀片表面宜由硬化 鋼所組成，或使用極硬之材料例如鑽石所被覆。 而且，使用複數刀片將具有該項優點，即可將隔板製成 大到5 0厘米的寬度，且在捲繞前，依照顧客要求，將完全 足夠用於許多型式的電池之數厘米的成品窄條，自此寬網 片上予以切下。此方式使該方法較任何隨後成品形成更爲 經濟。 本發明的方法，提供了特別使用爲電池中隔板之隔板。 使用本發明方法所製成之隔板，宜具有小於3 5 μηι厚度， 更宜小於25μηι，且最宜自10至25μιη。在連通至電解質之 該部份的隔板上薄的厚度保證了特別低的電阻，隔板本身 顯然具有極高的電阻，因爲其本身必須具有絕緣性質。 本發明的隔板包括多孔性電絕緣之陶瓷塗層。使存在於基 板上及其中’包含Al、Zr或Si等金屬的不導通氧化物之 塗層可能有利。隔板的孔隙度宜自3 0 %至8 0 %範圍內，更 宜自5 0 %至7 0 %範圍內。此處孔隙度係述及可進入，如開 口孔隙。在此意義上’孔隙度可經由汞孔隙計之熟悉方法 予以測定，或可自所使用之原料的體積和密度予以計算， 假定最適當的開口孔隙是存在的。 本發明的1½板可具有至少1 N / c m以上的斷裂強度，較佳 至少3 N / c m，更宜爲3至1 0 N / c m。本發明的隔板之任何彎 -26- 200405602 曲半徑至低於100mm以下爲佳而無損壞，較佳爲低至50m % ’最宜爲低至2mm。根據本發明隔板的高斷裂強度和良好 可彎曲性，其具有之優點爲：該隔板在電池的充電和放電 過程中’能依循著發生之電極幾何形狀變化，而隔板不致 損壞。再者，可彎曲性其具有之優點爲：使用此隔板可製 造商業標準化之捲繞電池組。關於此等電池組，使電極-隔 板層以相互螺旋方式而捲繞成標準化之大小並使其接觸。 本發明的隔板可使用於相當在等於停工溫度之高溫，即 基板或任何加成倂入之停工粒子的熔化溫度。根據本發明 所製造之隔板，適用於所有傳統式之電池中，尤其是原電 池組和蓄電池組（二次電池）。於使用時，通常將本發明的 隔板充塡一種適當電解質系統，其可能使離子可自電池的 電極一 W ’遷移通過隔板’至另一個電極。將本發明的隔 板充塡著包含鋰離子之電解質後，例如，該基板可使用作 爲鋰離子電池中之隔板。AMEO = 3-amine (propyl) propyltriethoxysilane DAMO = 2-amine (ethyl) ethyl-3-amine (yl) propyltrimethoxysilane GLYM 0 = 3-glycidyloxytrimethoxy Silane MEMO = 3-Methacryloxypropyltrimethoxysilane Silfin = Vinyl Silane + Initiator + Catalyst VTEO = Vinyl Triethoxy Silane VTMO = Vinyl Trimethoxy Silane VTMOEO = Vinyl Trimethoxy (2-methoxyethoxy) silane In a particular embodiment of the method according to the invention, in the previous step, the adhesion promoter described above is applied to a substrate, in particular to a polymerized non-woven fabric. For this reason, the adhesion promoter is dissolved in a suitable solvent such as ethanol. This solution may additionally include a small amount of water (preferably 0.5 to 10 times the number of moles of hydrolyzable groups) and a small amount of an acid, such as HC 1 -21-200405602 or Η Ν Ο 3 for hydrolysis and condensation si -0 Catalyst for R group. This solution is applied to the substrate by familiar techniques, for example, spraying on it, printing on it, pressing on it, pressing into it, rolling on it, applying a doctor blade on it, covering it on It is impregnated, sprayed or poured on it, and the adhesion promoter is fixed on the substrate by heat treatment from 50 to not more than 350 t. Only after the adhesion promoter is applied, according to this specific embodiment of the method of the invention, a suspension is applied and cured. Prior to the actual application of the suspension, the application of adhesion promoters can provide substrates with improved adhesion, especially with respect to aqueous particulate sols, which is why such pre-treated substrates can be particularly treated according to the present invention using commercially available sols such as A suspension of nitric acid sol or silica sol for coating. However, this way of applying an adhesion promoter also means that the manufacturing process of the separator according to the present invention must be expanded to include insertion or preliminary processing steps. Although it is more expensive and inconvenient than using available sols to which adhesion promoters have been added, this approach is still feasible and has the advantage that better results can be obtained when using commercial grade sol-supplyable suspensions. The coating according to the present invention is a suspension liquid which is cured in and on a substrate. According to the present invention, the suspension present on and in the substrate can be cured by heating to 50 ~ 350 ° C. Since the maximum temperature when using a polymeric substrate material is governed by the substrate used, it must be adapted to the maximum temperature. Therefore, according to a specific embodiment of the method of the present invention, the suspension present on the substrate and therein is cured by heating to 100 ~ 3 50 ° C, and most preferably to 1 1 ~ 2 8 0 ° C. It may be advantageous to heat to 100-350 ° C for 1 second to 60 minutes. More preferably, it is heated to 1 1 0 ~ 3 00. Since it is solidified and suspended -22-200405602 liquid, it is most suitable to be heated to 11 0 ~ 2 0 0 ° C, and it should be heated for 0.5 to 0 minutes, that is, heat treatment, especially It is performed at a temperature of at least 20 t below the softening temperature of the polymer material. Curing the separator according to the selected temperature range, some polymer materials may cause changes in their chemical structure under the influence of heat, so that these polymers will no longer exist in their original state or variants. For example, polyimide may be partially carbonized, while polyacrylonitrile may form a so-called ladder polymer, which then undergoes partial carbonization. These influences can often lead to changes in the properties of the carrier material. According to the invention ' it can be heated by heated air, hot air, infrared radiation or by a combination of other heating methods according to the prior art. The continuous procedure according to the present invention is preferably performed by the following operations, unrolling the substrate from a roller at a rate of lm / h to 2m / s (preferably from 0.5ni / min to 20m / min, Optimally at a rate from lm / min to 5 m / niin) to pass through at least one device (such as a roller), which applies the suspension on and into the carrier, and through at least one other device, which passes the suspension through Heating, for example, using an electric furnace, is cured on and in the carrier 'and the separator thus produced is wound on a second roll. This operation makes it possible to manufacture the separator according to the present invention in a continuous process. Similarly, by observing the parameters described, the pretreatment procedure can be performed on a continuous basis. As mentioned earlier, 'the procedure must be performed in such a way that during the coating operation or during each operation', especially during the heat treatment (drying), the substrate has a maximum tension of lON / cm in the longitudinal direction, preferably not more than 3N / Cm, It is best not to exceed 0.1 N / cm. In this regard, the term "coating operation" refers to all processing steps-23-200405602, in which the material is brought onto and into a substrate and cured by heat treatment thereon. During the coating operation, the The substrate is stretched with a maximum force of 0.001 to 3 N / cm. It may be particularly expedient that the substrate is not actually stretched in the longitudinal direction during the coating operation or operations. In order to prevent deformation of the carrier material, or even elastic deformation, the traction tension must be controlled very precisely. Since excessive traction tension may deform (stretch), it may mean that the ceramic coating cannot follow the structured material, with the result that the coating can become separated from the substrate material over a large area. The resulting product cannot be used for its intended purpose. It is obviously not feasible to pay attention to the coating limitation of the above-mentioned polymeric substrate material having porous ceramics. In order to control or set the tension, it is determined to be advantageous to guide the substrate onto at least two rolls or rollers during the coating operation. The roller (s) or rollers should be equipped with a drive ' and the speed of rotation of the two rollers or rollers should be separate and controllable. Additional rollers may be present between the two rollers or rollers. The additional rollers do not have to be driven, but can be configured as pure support rollers, which can be easily rotated on rollers or rollers. But making these rollers, each with its own drive ' separable, controllable and possibly also advantageous. The rollers can be configured in such a way that the substrate moves vertically, horizontally, or at any other desired angle relative to gravity. The substrate is preferably moved vertically or horizontally. Both directions have their advantages and disadvantages. When the substrate is moved vertically during the application and bonding of the coating material and during the subsequent curing of the material, the substrate cannot sag between the two rolls and therefore undergoes uncontrolled stretching during the application of the coating material. Because of its own weight, it is necessary to avoid any longitudinal stretching of the material. If it is to be guided vertically, it must be -24-200405602. After applying the coating material, the substrate must be guided to leave the curing device. (Usually an oven). It has been determined that with regard to the procedure of the invention to be carried out, it is particularly advantageous to 'maintain the substrate in a tenter during the coating operation, and especially during heat treatment, using a tenter to ensure that the substrate does not It will be over-tensioned. For this purpose, the tenter has a lateral guide, which supports the substrate during the coating operation. The guidance in the tenter frame also protects any normal shrinkage of the mesh that occurs during the heat treatment process and will be uniquely reflected in the thickness of the mesh, rather than in the vertical dimension of the material. The tenter is more preferably provided with a side guide, which has moving auxiliary equipment, and should be equipped with an adjustable drive. The movement assisting device should be engaged or clamped in the base plate, and can be moved at a selected speed. A possible specific embodiment of such a tenter is a speed consisting of two driven rollers or rolls, which can be adjusted. Between these rollers, there is a chain or belt that runs at the speed of the rollers on one or both ends of the rollers. These chains or straps are arranged at regular intervals and can engage the auxiliary equipment in the substrate. Such auxiliary equipment may be, for example, a (short) sheath, clip, or similar device that can be engaged into a substrate. In order that the auxiliary equipment can have a sufficient fulcrum on the substrate, it has been determined that it is advantageous to engage the auxiliary equipment into the substrate at a distance of 0.2 to 2 cm from the edge of the substrate mesh. In order to obtain a uniformly distributed force, it has been determined that it is particularly advantageous to make the auxiliary equipment engage on each side of the substrate so as to have a uniform distribution. This phenomenon can be achieved by the continuous or agitation of the auxiliary equipment in the base plate, the interval range is 0 (continuous) to 15 cm, and preferably 1 to 10 cm. -25-200405602 In a preferred variant, before winding the separator, the defective edge area formed by the tenter and cannot be used in the battery is directly and continuously removed. This operation should be performed by fixed or rotating blades. Since the blade is quickly passivated by cutting the ceramic spacer, the cutting spacer cannot be sharpened anymore. The surface of the blade should be composed of hardened steel or covered with extremely hard materials such as diamond. Moreover, the use of multiple blades will have the advantage that the separator can be made up to a width of 50 cm, and before winding, according to customer requirements, it will be completely sufficient for a few cm of finished products of many types of batteries Narrow strips, cut from wide mesh since then. This approach makes the method more economical than any subsequent finished product formation. The method of the present invention provides a separator especially used as a separator in a battery. The separator made by the method of the present invention should preferably have a thickness of less than 3 5 μm, more preferably less than 25 μm, and most preferably from 10 to 25 μm. The thin thickness on the separator connected to this part of the electrolyte ensures a particularly low resistance, and the separator itself obviously has extremely high resistance because it itself must have insulating properties. The separator of the present invention includes a porous electrically insulating ceramic coating. It may be advantageous to have a coating of non-conductive oxides ' containing metals such as Al, Zr, or Si present on and in the substrate. The porosity of the separator should be in the range of 30% to 80%, and more preferably in the range of 50% to 70%. Here porosity refers to accessibility, such as open porosity. In this sense, the 'porosity can be determined by the familiar method of a mercury porometer, or it can be calculated from the volume and density of the raw materials used, assuming that the most appropriate open porosity exists. The 1½ sheet of the present invention may have a breaking strength of at least 1 N / cm, preferably at least 3 N / cm, and more preferably 3 to 10 N / cm. Any bend of the separator of the present invention is preferred to have a radius of curvature of less than 100 mm without damage, preferably as low as 50 m%, and most preferably as low as 2 mm. According to the separator of the present invention, the high breaking strength and good bendability have the advantage that the separator can follow the geometrical shape of the electrode during charging and discharging of the battery without causing damage to the separator. Furthermore, the flexibility has the advantage that a commercially standardized wound battery can be manufactured using this separator. With regard to these battery packs, the electrode-separator layer is wound in a spiral manner with each other to a standardized size and brought into contact. The separator of the present invention can be used at a temperature as high as the shutdown temperature, i.e., the melting temperature of the substrate or any additive-infused shutdown particles. The separator manufactured according to the present invention is suitable for all conventional batteries, especially primary batteries and secondary batteries (secondary batteries). In use, the separator of the present invention is usually charged with a suitable electrolyte system, which may allow ions to migrate from the battery's electrode W 'through the separator' to another electrode. After the separator of the present invention is filled with an electrolyte containing lithium ions, the substrate can be used as a separator in a lithium ion battery, for example.
本發明亦提供含有根據本發明之隔板的電池，例如，此 等電池可能是鋰離子電池、鎳金屬氫化物電池、鎳-鎘電池 、銀-鋅電池或鋅-空氣電池。此類電池中特佳是鋰離子電 池。本發明的隔板對於欲快速予以充電之電池中極爲有用 。由於根據本發明的隔板具高耐熱性，配置此隔板之電池 並非過度熱敏感，而因此其能承受快速充電（所產生）之溫 度上昇而不會使隔板作不利的變化，或不會造成電池損壞 。而且，由於隔板其薄的厚度和高的孔隙度，而可能爲較 大之電流密度，以致增加負載容量。因此此等電池使用1 C -27- 200405602 的充電率（在一小時內可將電池的全部容量充滿）或亦可能 高達2 C。當使用如此配置之電池在電動車輛，其具有明顯 的優點，因爲此等電池可長時間使用而再加以充電，且在 相當短時間內即完成充電。 以下列爲本發明之不具限制性的實例。 實例1 :製造S 4 5 0 PET之隔板 將15克的5重量％HC1水溶液、10克的四乙氧基矽烷、 2.5克的甲基三乙氧基砂烷及7.5克的GlymoDynasilane (係由 Degussa公司所造之所有Dynasilanes)首先加入於 1 6 0克的乙醇中。然後使用剛開始攪拌了歷數小時之此溶 膠，以懸浮每種125克來自Martinswerke公司之Martoxid MZS-1和Martoxid MZS-3礬土。將上述形成之泥漿，用磁 石攪拌器使其均化，再歷至少24小時，在此段期間內，爲 了使溶劑不致逸出，必須蓋住攪拌容器。 然後使用此泥漿，在大約3 0 m / h的帶速率和T = 2 0 0 °C下 於連續輥塗程序中，塗覆在由Freudenberg公司所製所PET 非織物，使其塗層具有56厘米厚度、大約30微米厚度及 大約20g/m2基重。在此輥塗程序中，將泥漿使用於平行帶 方向旋轉之一只輥（非織物的移動方向），使其塗覆在非織 物上。隨後使該非織物，以所述溫度下，通過循環空氣烘 箱。網網片張力，在退繞機與塗覆站間，維持大約1 〇 N之 受力’而在塗覆站與上行絡筒機間，則是大約3 0N。 -28 - 200405602 實例2:製造S240 PAN之隔板 將15克的5重量％HC1水溶液、1〇克的四乙氧基矽烷、 2.5克的甲基三乙氧基矽烷及7.5克的GlymoDynasilane 首先加至1 6 0克的乙醇中。然後使用剛開始攪拌數小時之 此溶膠，來懸浮2 8 0克的AlCoA CT 1 2 0 0 SG礬土。 將此泥漿用磁石攪拌器，使其均化再經24小時，於此段 時間，爲使溶劑不致逸出必須蓋住攪拌容器。 然後使用此泥漿，以實例1所述之連續輥塗程序中，於 大約30m/h的帶速率和T = 2 5 0 °C下，塗覆在PAN非織物上 (來自Freudenberg公司之Viledon 1773)，使其具有56厘 米厚度、大約180微米厚度及大約22g/m2基重。最終所獲 結果是具有240奈米平均孔徑的隔板。 實例3 :製造S4 5 0 PO之隔板 將1 5克的5重量％HCi水溶液、1 0克的四乙氧基矽烷、 2.5克的甲基二乙氧基5夕院及7.5克的GlymoDynasilane 首先加至1 6 0克的乙醇中。然後使用剛開始攪拌數小時之 此溶膠，來懸浮每種125克的Martoxid MZS-1和Martoxid MZS-3礬土。將此泥漿’用磁石攪拌器，使其均化再經24 小時，在此段時間，爲使溶劑不致逸出必須蓋住攪拌容器。 將5 6厘米寬度、大約3 0微米厚度之p 〇非織物（來自 Freudenberg公司之FS 2202-03)，以自實例1所述之連續 輥塗程序中’於大約3 0 m / h的帶速率和T = 1 1 〇 °C下，以上 述之泥漿塗覆在非織物上。最終所獲結果是，其具有4 5 〇 奈米的平均孔徑之隔板。 - 29- 200405602 實例4 :製造S100 PET之隔板 將15克的5重量％HC1水溶液、10克的四乙氧基矽烷、 2.5克的甲基三乙氧基ί夕院及7.5克的GlymoDynasilane 首先加至1 6 0克的乙醇中。然後使用剛開始攪拌數小時之 此溶膠，來懸浮2 8 0克的AlCo A CT 3 0 0 0礬土。將此泥漿 ，用磁石攪拌器，使其均化再經24小時，在此段時間，爲 使溶劑不致逸出必須蓋住攪拌容器。 然後將56厘米寬度、大約30微米厚度及大約20 g/m2 基重之PET非織物，在連續輥塗程序中，以大約60m/h的 帶速率和T = 20(TC下，使用該泥漿塗覆於非織物上。乾燥 實際上是以無張力式予以完成，當它在烘箱的區域中時， 雖然有使用拉幅機來支持非織物。經過烘箱前，將拉幅機 釘在網片上之左和右，然後於烘箱之後再將它移開。在捲 繞前，將多孔之邊緣區域，用旋轉之刀片加以切除。最終 所獲結果是具有1 〇 〇奈米的平均孔徑之隔板。 實例5 :製造S100 PAN之隔板 將1 5克的5重量％ H C 1水溶液、1 〇克的四乙氧基矽烷、 2.5克的甲基三乙氧基矽烷及7.5克的GlymoDynasilane 首先加至1 6 0克的乙醇中。然後使用剛開始攪拌數小時之 此溶膠，來懸浮3 0 0克的A 1 C 〇 A C T 3 0 0 0 S G礬土。將此 泥漿，用磁石攪拌器，使其均化再經2 4小時’在此段時間 ，爲使溶劑不致逸出必須蓋住攪拌容器。 然後使用此泥發，以實例4所述之連續輥塗程序中’於 大約60m/h的帶速率和T = 2 5 0 °C下，來塗覆PAN非織物 -30- 200405602 (來自Freudenberg公司之Viledon 1773)，並使其具有56 厘米厚度、大約180微米厚度及22 g/m2基重。最終所獲結 果是具有1 0 0奈米的平均孔徑之隔板。 實例6 :製造S 4 5 0 PAN之隔板 將1 5克的5重量％ H C 1水溶液、1 〇克的四乙氧基矽烷、 2.5克的甲基二乙氧基石夕院及7.5克的MEMO Dynasilane 首先加至1 6 0克的乙醇中。然後使用剛開始攪拌歷數小時 之此溶膠，來懸浮每種1 4 0克M a r t ο X i d Μ Z S - 1和M a r t ο X i d MZS-3礬土。將此泥漿，用磁石攪拌器使其均化再經24小 時，在此段時間，爲使溶劑不致逸出必須蓋住攪拌容器。 然後使用此泥漿，以實例4所述之連續輥塗程序中，於 大約1 20m/h的帶速率和T = 2 5 0 °C下，來塗覆PAN非織物 (來自Freudenberg公司之Viledon 1773)，使其具有56厘 米厚度、大約1 80μηι)微米厚度及22g/m2基重。最終所獲 結果是具有4 5 0奈米的平均孔徑之隔板，其具有較依照實 例2隔板上之塗層更佳的塗層黏著性。 實例7 :製造S 4 5 0 PET之隔板 將3 0克的5重量％ H C 1水溶液、1 〇克的四乙氧基矽烷、 2.5克的甲基二乙氧基5夕院及7.5克的GlymoDynasilane 首先加至1 3 0克的水和3 0克的乙醇中。然後使用剛開始攪 拌數小時之此溶膠，來懸浮每種1 2 5克M art ο X i d Μ Z S - 1和 Mart oxi d MZS-3礬土。將此泥漿，用磁石攪拌器使其均化 ，再經24小時，在此段時間，爲使溶劑不致逸出必須蓋住 攪拌容器。 200405602 將56厘米莧度、大約13微米厚度及約gg/m 2基重之pet 非織造物’於貫例1所述之連續輕塗程序中，以大約3 0 m / h 的帶速率和T = 2 0 0 °C下，使用上述泥漿塗覆。最終所獲結 果是具有4 5 0奈米的平均孔徑之隔板，其具有極佳之黏著 性及較實例1中所述之隔板所具大約3 0微米，更低之厚度。 實例8 :製造Z4 5 0 PAN之隔板 將1 0克7 0重量％丙醇銷的丙醇溶液，溶於3 4 0克之丙 醇中。經由劇烈攪拌，將此溶液與0.7 2克之水和〇 · 〇 4克 之濃氫氯酸摻合。繼續攪拌此溶膠數小時。 然後用此溶膠，在連續輥塗程序中，以大約8 m/h的帶速 率和T = 200°C下，來塗覆PAN非織物（來自Freudenberg公 司，Viledon 1773)使其具有大約1〇〇微米厚度和22g/m2基 重。 將1 · 4克之乙醯丙酮酸銷溶於1 5 0克去離子水和2 2.5克 乙醇的混合物中。將每種1 4 0克MZ S - 1和MZ S - 3於此溶液 中懸浮，並將尼漿攪拌至少2 4小時。在塗覆步驟大約1 小時前，將另外75克的商業級30重量％硝酸銷，MEL化 學公司所製之溶膠加至此泥漿中。 然後將5 6厘米寬度，預塗之PAN非織物，以實例1所 述之第二連續輥塗程序中，於大約60m/h之帶速率和T = 2 5 0 °C 下，以此泥漿塗覆之最終所獲結果是具有4 5 0奈米的平均 孔徑之隔板，其具有，甚至在極爲鹼性的介質（pH> 10)中亦 然富極佳之黏著性和優良之穩定性。 依照實例1至8，所有本發明製造之隔板，其較傳統式 200405602 所製造之隔板，明顯地顯示出降低了缺陷之出現率，其中 在製造期間，其容許基板有大於ION/cm的牽引張力。此 亦經由下文中所測定之Gurley數値予以證實。在習知所製 造之陶瓷隔板的情況中，因爲缺之出現率十足，而經常不 能測定Gurley數値。習知所製造之隔板的缺陷出現率尤其 由於隔板的收縮，該收縮（率）顯然高於2%，經常在 5%至 15 %間。此種高收縮（率）導致陶瓷塗層與基板分離。在根據 本發明所製造之隔板中，不仗用拉幅機下，可獲得經由遵 守在縱方向小於1 0 N / c m的牽引張力，在基板有2 %的最大 收縮率。使用拉幅機所製成之隔板，如實例4、5和6等實 例中並無收縮。 實例9 :本發明隔板的Gurley數値 下表2中所槪括之Gurley數値，係由g. Venug opal; J. of P o w e ι· S o u r c e s 7 7 ( 1 9 9 9 ) 3 4 - 4 1中所述方法對於實例；[至8 的各種隔板所測得。The present invention also provides batteries containing the separator according to the present invention. For example, these batteries may be lithium ion batteries, nickel metal hydride batteries, nickel-cadmium batteries, silver-zinc batteries, or zinc-air batteries. Particularly preferred among these batteries are lithium-ion batteries. The separator of the present invention is extremely useful in a battery to be quickly charged. Due to the high heat resistance of the separator according to the present invention, the battery configured with the separator is not excessively thermally sensitive, and therefore it can withstand the temperature rise of the rapid charge (generated) without adversely changing the separator, or It may damage the battery. Moreover, due to the thin thickness and high porosity of the separator, it may have a large current density, which increases the load capacity. Therefore, these batteries use a charge rate of 1 C -27- 200405602 (the full capacity of the battery can be fully charged in one hour) or it may be as high as 2 C. When using such a battery in an electric vehicle, it has obvious advantages, because these batteries can be recharged for a long time and can be charged in a relatively short time. The following are non-limiting examples of the invention. Example 1: S 4 50 0 PET separator. 15 g of a 5% by weight aqueous solution of HC1, 10 g of tetraethoxysilane, 2.5 g of methyltriethoxy sarane, and 7.5 g of GlymoDynasilane (made by All Dynasilanes made by Degussa were first added to 160 grams of ethanol. This gel, which had just been stirred for several hours, was then used to suspend 125 grams of each of Martoxid MZS-1 and Martoxid MZS-3 alumina from Martinswerke. The slurry formed as described above was homogenized with a magnetic stirrer for another 24 hours. During this period, the stirring container must be covered in order to prevent the solvent from escaping. This slurry was then used in a continuous roll coating procedure at a belt speed of approximately 30 m / h and a T = 200 ° C, to a PET nonwoven made by Freudenberg, with a coating of 56 Thickness of centimeters, thickness of about 30 microns and basis weight of about 20 g / m2. In this roller coating procedure, the slurry is applied to a non-woven fabric by rotating one of the rollers in the direction of the parallel belt (the direction of movement of the non-woven fabric). The non-woven fabric was then passed through a circulating air oven at said temperature. The tension of the mesh sheet is maintained at a force of about 10 N ′ between the unwinding machine and the coating station, and about 30 N between the coating station and the upward winder. -28-200405602 Example 2: Manufacture of S240 PAN separator 15 grams of 5% HC1 aqueous solution, 10 grams of tetraethoxysilane, 2.5 grams of methyltriethoxysilane and 7.5 grams of GlymoDynasilane To 160 grams of ethanol. This sol, which had just been stirred for several hours, was then used to suspend 280 grams of AlCoA CT 1220 SG alumina. This slurry was homogenized with a magnetic stirrer for another 24 hours. During this time, the stirring container must be covered to prevent the solvent from escaping. This slurry was then applied to a PAN non-woven fabric (Viledon 1773 from Freudenberg) at a belt speed of approximately 30 m / h and T = 250 ° C in the continuous roll coating procedure described in Example 1. It has a thickness of 56 cm, a thickness of about 180 microns, and a basis weight of about 22 g / m2. The end result was a separator with an average pore size of 240 nm. Example 3: Manufacture of S4 50 PO separator 15 grams of 5% by weight aqueous solution of HCi, 10 grams of tetraethoxysilane, 2.5 grams of methyl diethoxy oxaline and 7.5 grams of GlymoDynasilane Add to 160 grams of ethanol. This sol was then used for a few hours of stirring to suspend 125 g of each of Martoxid MZS-1 and Martoxid MZS-3 alumina. This slurry 'was homogenized with a magnetic stirrer for another 24 hours. During this time, the stirring container must be covered in order to prevent the solvent from escaping. A 56-cm-wide p 30 non-woven fabric (FS 2202-03 from Freudenberg) was applied at a belt rate of about 30 m / h in the continuous roll coating procedure described in Example 1. And T = 1 10 ° C, the non-woven fabric was coated with the above slurry. The final result was a separator with an average pore size of 450 nm. -29- 200405602 Example 4: To manufacture S100 PET separator, 15g of 5% by weight HC1 aqueous solution, 10g of tetraethoxysilane, 2.5g of methyltriethoxyl and 7.5g of GlymoDynasilane Add to 160 grams of ethanol. This sol was then used for just a few hours to suspend 280 grams of AlCo A CT 3 00 alumina. This slurry was homogenized with a magnetic stirrer for another 24 hours. During this time, the stirring container must be covered to prevent the solvent from escaping. Then, a PET nonwoven fabric with a width of 56 cm, a thickness of about 30 microns, and a basis weight of about 20 g / m2 was used in a continuous roll coating process at a belt speed of about 60 m / h and T = 20 (TC, using the slurry coating Covering on non-woven fabrics. Drying is actually done tension-free. When it is in the area of the oven, tenter frames are used to support the non-woven fabrics. Before passing through the oven, nail the tenter frame to the mesh. Left and right, then remove it after the oven. Before winding, cut off the porous edge area with a rotating blade. The final result is a separator with an average pore size of 1000 nm. Example 5: Manufacture of S100 PAN separator 15 grams of 5 wt% HC1 aqueous solution, 10 grams of tetraethoxysilane, 2.5 grams of methyltriethoxysilane and 7.5 grams of GlymoDynasilane were first added to 1 60 grams of ethanol. Then use this sol for a few hours to suspend 300 grams of A 1 CO ACT 3 0 0 0 SG alumina. Use a magnetic stirrer to mix this slurry and make it homogeneous. After another 24 hours', during this time, it is necessary to prevent the solvent from escaping. Hold the stirring container. Then use this mud to coat the PAN non-woven fabric at the belt speed of about 60 m / h and T = 25 0 ° C in the continuous roll coating procedure described in Example 4-30-200405602 (Viledon 1773 from Freudenberg) and made it 56 cm thick, about 180 microns thick and 22 g / m2 basis weight. The final result was a separator with an average pore size of 100 nm. Example 6: To manufacture the S 4 50 PAN separator, 15 grams of a 5% by weight aqueous solution of HC 1, 10 grams of tetraethoxysilane, 2.5 grams of methyl diethoxyl oxaline, and 7.5 grams of MEMO Dynasilane were first added. To 160 grams of ethanol. Then use this sol that has just been stirred for several hours to suspend each of 140 grams of M art ο X id Μ ZS-1 and M art ο X id MZS-3 alumina. This slurry was homogenized with a magnetic stirrer for another 24 hours. During this time, the stirring container must be covered to prevent the solvent from escaping. Then, using this slurry, in the continuous roll coating procedure described in Example 4, Coat PAN non-woven fabric (from Freudenberg Co., Ltd.) at a belt speed of approximately 1 20 m / h and T = 250 ° C. The Viledon 1773), to have a 56 cm thickness, about 1 80μηι) micron thickness and 22g / m2 basis weight. The final result was a separator with an average pore size of 450 nm, which had better coating adhesion than the coating on the separator according to Example 2. Example 7: Production of a separator for S 4 50 PET 30 grams of a 5% by weight aqueous solution of HC 1, 10 grams of tetraethoxysilane, 2.5 grams of methyl diethoxy, and 7.5 grams of GlymoDynasilane was first added to 130 grams of water and 30 grams of ethanol. This sol, which had just been stirred for several hours, was then used to suspend each of the 125 grams of each of M art ο X d Μ Z S-1 and Mart oxid d MZS-3 alumina. The slurry was homogenized with a magnetic stirrer, and after another 24 hours, the stirring container must be covered in order to prevent the solvent from escaping. 200405602 A non-woven fabric of 56 cm in thickness, a thickness of about 13 microns and a basis weight of about gg / m 2 was used in the continuous light coating procedure described in Example 1 at a belt speed of about 30 m / h and a T = 2 0 0 ° C, coated with the above mud. The final result is a separator with an average pore size of 450 nm, which has excellent adhesion and a thickness of about 30 microns, which is lower than that of the separator described in Example 1. Example 8: Manufacturing of a separator for Z4 50 PAN 10 g of a 70% by weight solution of propanol sold in propanol was dissolved in 340 g of propanol. With vigorous stirring, this solution was blended with 0.7 2 g of water and 0.04 g of concentrated hydrochloric acid. Continue to stir the sol for several hours. This sol was then used to coat a PAN non-woven fabric (from Freudenberg Company, Viledon 1773) at a tape speed of approximately 8 m / h and a tape speed of about 8 m / h in a continuous roll coating procedure to a value of about 100. Micron thickness and 22g / m2 basis weight. 1.4 g of acetamidine pyruvate was dissolved in a mixture of 150 g of deionized water and 2 2.5 g of ethanol. Each of 140 grams of MZ S-1 and MZ S-3 was suspended in this solution, and the paste was stirred for at least 24 hours. About one hour before the coating step, another 75 grams of a commercial grade 30% by weight nitric acid pin, a sol made by MEL Chemical Co., was added to the slurry. Then apply a PAN non-woven fabric with a width of 56 cm in the second continuous roll coating procedure described in Example 1 at a belt speed of about 60 m / h and T = 2 50 ° C. The final result of the coating is a separator with an average pore size of 450 nm, which has excellent adhesion and excellent stability even in extremely alkaline media (pH > 10). According to Examples 1 to 8, all the separators manufactured by the present invention showed significantly lower defect occurrence rates than the separators manufactured by the traditional 200405602, wherein during manufacturing, it allowed the substrate to have a greater than ION / cm. Traction tension. This was also confirmed by the Gurley number determined below. In the case of conventionally manufactured ceramic separators, it is often not possible to measure the Gurley number because of the high incidence of defects. The defect occurrence rate of the separators manufactured by the conventional is especially due to the shrinkage of the separators, which is obviously higher than 2%, often between 5% and 15%. This high shrinkage (rate) causes the ceramic coating to separate from the substrate. In the separator manufactured according to the present invention, it is possible to obtain a maximum shrinkage of 2% on the substrate by observing a traction tension of less than 10 N / cm in the longitudinal direction without using a tenter. The separator made of the tenter, as in Examples 4, 5 and 6, did not shrink. Example 9: Gurley number of the separator according to the present invention. The Gurley number included in Table 2 below is by g. Venug opal; J. of Power · S ources 7 7 (1 9 9 9) 3 4- The method described in 41 is for the example; measured with various separators [to 8].
表2 實例 材料 Gurley數値 1和7 S450 PET 2 8 Z450 PAN 3 6 S450 PAN 3 3 S450 PO 2.5 2 S240 PAN 4 4 S 1 00 PET 8 5 S 1 00 PAN 1 2 -33- 200405602Table 2 Example Materials
實例10:具有ZZ24 0 PAN 將10克，70重量％丙醇鍩的丙醇溶液溶於3 4 0克之丙醇 中。將此溶液與0.7 2克之水和0 · 0 4克之濃氫氯酸摻合， 每次添加均予劇烈攪拌。其後，再繼續攪拌此溶膠若干 (或數）小時。 使用此溶膠，在連續輥塗程序中，以大約8 m/h之帶速率 和T = 2 0 0 °C下，塗覆PAN非織物，使其具有大約50微米 厚度和大約25g/m2基重。 將1.4克的乙醯丙酮酸鉻，溶入1 5 0克去離子水和2 2.5 克乙醇的混合物中。將2 8 0克之S C 1 0 5氧化鉻於此溶液中 懸浮，並將該尼漿攪拌24小時。在塗覆步驟大約1小時前 ，將額外75克的商業級30重量％硝酸鉻MEL化學公司所 製之溶膠加至此泥漿中。 然後將該預塗之PAN非織物，於第二連續輥塗程序中， 以大約8m/h之帶速率和T = 2 5 0 °C下，用此泥漿塗覆之最終 結果是具有4 5 0奈米的平均孔徑之隔板，其具有極佳黏著 性和極佳穩定性，甚至在極爲鹼性介質（p Η > 1 0 )中亦然。 因此此隔板在Ni/MeH或Ag/Zn電池中極爲有用。此等電 池具有至少1 〇 〇充電週期的長期穩定性。 實例11 :具有混合型陶瓷隔板之鋰離子電池 將依照實例7所製造之S 4 5 0 PET隔板安裝在鋰離子電池 中，此電池係由L i C 〇 0 2之正質量、由石墨所組成之負質量 及碳酸伸乙基酯/碳酸二甲酯中LiPF6所組成之電解質所組 成[1^(：〇02//3-450-?£丁、£(：/0^1<：1]，11\/[1^??6//石墨]。 -34- 200405602 試驗此電池的充電性狀，在超過2 5 0週期後，該電池之負 載容量僅極微地降低，大約數個百分點。在第2 0 0次充電 循環時甚至增加4 . 1至4.2伏特充電電壓，對該電池無損 害 ° (五）圖式簡單說明：無Example 10: ZZ24 0 PAN A solution of 10 g of a 70% by weight solution of propanol in propanol was dissolved in 340 g of propanol. This solution was blended with 0.7 2 g of water and 0.44 g of concentrated hydrochloric acid, and each addition was vigorously stirred. Thereafter, the sol was continued to be stirred for a few more hours. Using this sol, in a continuous roll coating process, a PAN non-woven fabric was coated at a tape speed of about 8 m / h and T = 200 ° C to have a thickness of about 50 microns and a basis weight of about 25 g / m2. . 1.4 grams of chromium acetamidine pyruvate was dissolved in a mixture of 150 grams of deionized water and 2 2.5 grams of ethanol. 280 g of Sc 105 chromium oxide was suspended in this solution, and the paste was stirred for 24 hours. Approximately 1 hour before the coating step, an additional 75 grams of a commercial grade 30% by weight chromium nitrate sol made by MEL Chemical Company was added to the slurry. The pre-coated PAN non-woven fabric was then coated with the slurry in a second continuous roll coating process at a belt speed of approximately 8 m / h and T = 2 50 ° C. The final result was 4 50 The separator with an average pore size of nanometers has excellent adhesion and stability, even in extremely alkaline media (p Η > 10). This separator is therefore extremely useful in Ni / MeH or Ag / Zn batteries. These batteries have a long-term stability of at least 1,000 charge cycles. Example 11: Lithium-ion battery with hybrid ceramic separator The S 4 50 0 PET separator manufactured according to Example 7 was installed in a lithium-ion battery. This battery was made of graphite with a positive mass of L i C 〇 2 and made of graphite. The negative mass of the composition and the electrolyte composed of LiPF6 in ethylene carbonate / dimethyl carbonate [1 ^ (: 〇02 // 3-450-? £ ding, £ (: / 0 ^ 1 <: 1], 11 \ / [1 ^ ?? 6 // graphite]. -34- 200405602 Tested the battery's charging characteristics. After more than 250 cycles, the load capacity of the battery decreased only slightly, about a few percentage points. .In the 200th charge cycle, even increase the charging voltage from 4.1 to 4.2 volts, which will not damage the battery.
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