TWI837512B - 塗覆液組成物、附塗覆膜之基材、分隔膜、二次電池及電極材料 - Google Patents
塗覆液組成物、附塗覆膜之基材、分隔膜、二次電池及電極材料 Download PDFInfo
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- TWI837512B TWI837512B TW110134587A TW110134587A TWI837512B TW I837512 B TWI837512 B TW I837512B TW 110134587 A TW110134587 A TW 110134587A TW 110134587 A TW110134587 A TW 110134587A TW I837512 B TWI837512 B TW I837512B
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- 239000004711 α-olefin Substances 0.000 description 1
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Abstract
本發明提供主要包含高分子之塗料、墨水、接著劑、鋰離子電池之正極、負極、分隔膜等之塗覆液,即使加熱時亦不易變形之塗覆液組成物。
本發明之塗覆液組成物之特徵係包含填料、溶劑、分散劑、增黏劑,塗覆於基材形成0.5~20μm厚之塗覆膜時,塗覆膜於200℃、15分鐘之收縮率為20.0%以下。
Description
本發明有關包含填料、溶劑、分散劑及增黏劑之塗覆液組成物及包含本發明之塗覆液組成物之附塗覆膜之基材者,且有關主要包含高分子之塗料、墨水、接著劑、鋰離子電池之正極、負極、分隔膜等之塗覆液中,形成即使施加熱時亦不易變形之塗覆膜的塗覆液組成物。
基於工業領域全面之環境面及安全面之觀點及效率性,而使用組成物之塗覆、印刷技術已廣泛被使用。
但是,無法掌握有助於對基材保持一定空隙率之塗膜之耐熱性及形狀維持的因子。
於專利文獻1,藉由將以離子交換水稀釋纖維狀纖維素之懸浮液設為特定之TI值(搖變性指數),而提高電池用分隔膜塗液之分散性及塗覆容易性。但是,並未揭示包含纖維狀纖維素及離子交換水以外之組成物之狀態的TI值,又針對有助於耐熱性之因子並未記載亦未教示。
於專利文獻2,雖揭示塗覆性優異、可形成均勻塗膜之塗液,但係塗液中之水溶性成分的含量為5%以下及相對於水溶性成分固形分較多之狀態之塗液。
該等專利文獻中,就耐熱性及變形性之觀點均完全未有任何教示。尤其是鋰離子二次電池等搭載於電動車等之情況,一般係設為萬一於異常發熱時超過塗覆膜所含之多孔質聚烯烴製薄膜之聚丙烯的結晶熔點,則使細孔徑縮小使鋰離子不通而抑制進一步發熱之構造,於溫度進一步上升之情況,分隔膜熔斷而產生破裂之溫度稱為熔斷溫度,於超過該熔斷溫度之情況聚烯烴製膜縮小,已知成為正極與負極短路並起火之原因。
[先前技術文獻]
[專利文獻]
[專利文獻1] 國際公開第2018/070473號
[專利文獻2] 日本專利第5829557號公報
[發明欲解決之課題]
若欲於加熱時可保持基材之形狀,且為了可防止上述問題點,本發明人等認為若限定塗覆膜之特性可解決上述課題,但塗覆膜及塗覆液宜具備何種特性則全然未明瞭。
[為了解決課題之手段]
該狀況下,本發明人等積極檢討之結果,發現自塗覆液於特定條件下形成塗覆膜時,藉由使塗覆膜之收縮率於特定範圍,可形成耐熱變形性優異,且表面平滑之塗覆膜,可充分使用於上述用途,因而完成本發明。
亦即,本發明之構成如以下。
[1] 一種塗覆液組成物,其包含填料、溶劑、分散劑、增黏劑、黏合劑,
塗覆於基材形成0.5~20μm厚之塗覆膜時,塗覆膜於200℃、15分鐘之收縮率為20.0%以下。
[2] 如[1]之塗覆液組成物,其中前述填料為塗覆液組成物之20質量%以上。
[3] 如[1]或[2]之塗覆液組成物,其中前述增黏劑係聚N-乙烯基羧醯胺。
[4] 如[1]至[3]之塗覆液組成物,其中前述增黏劑係聚N-乙烯基乙醯胺。
[5] 如[1]至[4]之塗覆液組成物,其中前述溶劑為水。
[6] 如[1]至[5]之塗覆液組成物,其中前述黏合劑係選自丙烯酸乳液、苯乙烯-丁二烯聚合物乳液之乳液。
[7] 如[1]至[6]之塗覆液組成物,其中前述基材係聚烯烴製薄膜。
[8] 如[7]之塗覆液組成物,其中前述聚烯烴製薄膜係選自聚乙烯、聚丙烯之至少一者。
[9] 如[7]或[8]之塗覆液組成物,其中前述聚烯烴製薄膜係聚丙烯、聚乙烯、聚丙烯之3層積層薄膜。
[10] 如[1]至[9]之塗覆液組成物,其中前述塗覆液組成物之填料/增黏劑之質量比係0.1~200。
[11] 如[1]至[10]之塗覆液組成物,其中前述增黏劑之黏度以原始黏度計為30mPa・s以上10000mPa・s以下。
[12] 一種附塗覆膜之基材,其包含由如[1]至[11]之塗覆液組成物形成之塗覆膜及基材。
[13] 一種分隔膜,其係由如[12]之附塗覆膜之基材所成。
[14] 一種二次電池,其係使用如[13]之分隔膜。
[15] 一種鋰離子二次電池,其係使用如[13]之分隔膜。
[16] 一種電極材料,其係於基材表面具備由如[1]至[11]之塗覆液組成物形成之塗覆膜。
[發明效果]
本發明之塗覆液組成物,因塗覆膜之熱變形小,故可抑制基材之變形,例如可作為汽車等之即使於高溫環境下亦不易變化之電極材料加以利用。該等技術若採用於二次電池,尤其是鋰離子二次電池等之電極及分隔膜等之塗覆膜,則可提高二次電池之發熱時之安全性。
以下,針對實施本發明之形態加以說明。
[塗覆液組成物]
本實施形態之塗覆液組成物包含填料、增黏劑、溶劑、分散劑、黏合劑。
此等塗覆液組成物,塗覆於基材及乾燥形成0.5~20μm之厚度之塗覆膜時,塗覆膜於200℃、15分鐘之收縮率為20.0%以下。
塗覆膜於200℃、15分鐘之收縮率為20.0%以下,較佳為15.0%以下,更佳為7.0%以下。塗覆膜於200℃、15分鐘之收縮率,較佳為0.01%以上,更佳為2.0%以上,又更佳為5.0%以上。收縮率係以於實施例記載之方法測定。收縮率若於前述範圍內,則耐熱性優異而較佳。
前述基材較佳為聚烯烴製薄膜,且更佳為選自聚乙烯、聚丙烯之至少一者。又基材較佳為聚丙烯、聚乙烯、聚丙烯之3層積層薄膜。薄膜之尺寸厚度無特別限制。
[填料]
填料可為無機填料亦可有機填料均無妨,但較佳為氧化鋁、勃姆石、滑石、高嶺土碳酸鈣、磷酸鈣、氧化鎂、非晶性氧化矽、結晶性玻璃填料、二氧化鈦、氧化矽-氧化鋁複合氧化物粒子、硫酸鋇、氟化鈣、氟化鋰、沸石、硫化鉬、雲母等之無機填料。其中,更佳為氧化鋁、勃姆石。
填料之形狀無特別限制,除了球狀、多面體狀、板狀、鱗片狀、柱狀、管狀以外,亦可為纖維狀。
填料為球狀及正多面體形狀以外之情況,填料之縱橫比,較佳為2以上,更佳為5以上,又更佳為10以上。若填料之縱橫比為2以上,則藉由填料之積層效果,可發揮於鋰樹狀晶體成長之情況下難以貫通分隔膜之效果。且,填料之縱橫比較佳為100以下。
填料之長徑較佳於0.1~1000μm,更佳於1~100μm之範圍。
填料之短徑,較佳於0.01~100μm,更佳於0.1~10μm之範圍。
於填料之體積基準之累積粒度分布之50%粒徑D
50,較佳於0.01~1000μm,更佳於0.1~100μm之範圍。
[增黏劑]
較佳的增黏劑可舉例聚N-乙烯基羧醯胺、聚N-乙烯基吡咯啶酮、羧甲基纖維素之鈉鹽、聚丙烯醯胺、聚乙烯醇、鹿角菜膠、三仙膠、瓜爾膠、果膠等之多糖類、羧甲基纖維素、羥甲基纖維素、羥乙基纖維素、甲基乙基羥基纖維素、甲基纖維素、羥丙基纖維素等之纖維素系聚合物、及該等纖維素系聚合物之銨鹽及鹼金屬鹽。
增黏劑較佳為聚N-乙烯基羧醯胺,更佳為聚N-乙烯基乙醯胺。若使用此等增黏劑,可形成熱變形性小的塗覆膜,可獲得塗覆表面外觀優異之塗覆膜。
作為構成聚N-乙烯基羧醯胺之單體,具體例舉例為N-乙烯基甲醯胺、N-乙烯基乙醯胺、N-乙烯基丙醯胺、N-乙烯基苯甲醯胺、N-乙烯基-N-甲基甲醯胺、N-乙烯基-N-乙基甲醯胺、N-乙烯基-N-甲基乙醯胺、N-乙烯基-N-乙基乙醯胺、N-乙烯基吡咯啶酮等。其中,基於塗覆性及與包含水之溶劑之親和性,特佳為N-乙烯基乙醯胺。
聚N-乙烯基羧醯胺可為均聚物亦可為共聚物。共聚合時,除了N-乙烯基羧醯胺以外,亦可共聚合丙烯腈、乙酸乙烯酯、丙烯酸、甲基丙烯酸、進而為丙烯酸、甲基丙烯酸、依康酸、馬來酸、巴豆酸等之鹽,但無特別限定。聚N-乙烯基羧醯胺中源自N-乙烯基乙醯胺之成分,較佳為60莫耳%以上。
增黏劑之黏度,以原始黏度(未調整溶液濃度)計,較佳為30mPa・s以上10000mPa・s以下。若於此範圍,塗覆容易進行而較佳。
[黏合劑]
黏合劑適宜為將苯乙烯-丁二烯樹脂及丙烯酸系樹脂等分散於水中之乳液或各種橡膠系之乳膠,其中,較佳為丙烯酸乳液、苯乙烯-丁二烯樹脂之乳液(苯乙烯-丁二烯共聚物乳液),更佳為交聯型之丙烯酸乳液。丙烯酸黏合劑可為均聚物亦可為共聚物。又,可直接使用乳液,亦可於固化後使用。
黏合劑相對於填料100質量份較佳為1質量份以上,更佳為2質量份以上,且相對於填料100質量份較佳為30質量份以下,更佳為7質量份以下。
[溶劑]
溶劑係分散或溶解上述各成分,且若為不反應者則無特別限定,但鑒於乾燥性,使用易揮發性之溶劑。具體而言,使用水或與水具有相溶性之極性溶劑,較佳包含水50質量%以上者,更佳僅為水。水特佳為離子交換水。作為水以外之溶劑,舉例為甲醇、乙醇、異丙醇等之醇類。水除了前述之乾燥性及各成分之分散及溶解能力外,因取得容易性而較佳。
[分散劑]
於本實施形態之塗覆液組成物中,根據需要,可包含分散劑。分散劑若為可將填料分散於溶劑則無特別限定,但較佳為十二烷基苯磺酸、聚乙烯醇、聚丙烯醯胺、聚甲基丙烯酸、高級醇環氧乙烷加成物、聚丙二醇環氧乙烷加成物、山梨醇及山梨醇酐之脂肪酸酯。作為鹽雖無特別限定,但作為鹽較佳不含金屬而為銨鹽。
包含分散劑之情況,其量相對於填料100質量份較佳為0.1質量份以上,更佳為0.5質量份以上。分散劑相對於填料100質量份較佳為5質量份以下,更佳為2質量份以下。若以該範圍含有,可提高填料之分散性。
本實施形態之塗覆液組成物中,塗覆液組成物中之填料之質量較佳於20~70質量%,更佳於25~60質量%,又更佳於40~50質量%之範圍。藉由以該等量含有填料,可形成熱變形性小的塗覆膜。
增黏劑與填料之質量比(填料/增黏劑),較佳為0.1以上200以下,更佳為30以上150以下,又更佳為60以上100以下。若為該比率,則可形成具有特定耐熱變形性之塗覆膜。
水等之溶劑,於前述塗覆液組成物中相當於前述成分之殘存部分,但通常相對於溶劑100質量份填料較佳為0.1~200質量份,更佳為40~100質量份。若為該範圍,則可獲得塗覆液組成物之良好流動性,塗覆性提高,且可提高所得之塗覆液之平滑性。
針對塗覆液組成物之各成分之混合方法無特別限定,但為了成為更均勻混合狀態,較佳至少將黏合
劑、增黏劑、分散劑分散於溶劑後添加填料並混合。又更佳至少將溶解有黏合劑、增黏劑、分散劑之溶液持續攪拌同時逐次添加填料並攪拌混合使之均勻化。藉此,可達到理想的混合狀態。又其他態樣中,首先於攪拌下於填料及溶劑中添加分散劑,將2次凝集解碎後,添加黏合劑、增黏劑,抑制再凝集同時將成分均勻混合。
本發明之塗覆液組成物,根據所調配之填料種類,可使用於塗料、墨水、接著劑、鋰離子電池之正極、負極、分隔膜等之各種塗覆液。
塗覆液組成物可直接作為塗覆液使用,但可根據需求,適當以溶劑等調整濃度及黏度作為塗覆液使用。
例如,藉由將前述塗覆液組成物塗布於基材表面並乾燥製造塗覆膜。又,亦可於基材表面具備由塗覆液組成物所成之塗覆膜(附塗覆膜之基材),作成電極材料。
又,塗覆液組成物包含增黏劑時,可提供乾燥時間顯著縮短之塗覆.乾燥方法。
塗覆液組成物對基材之塗覆方法無特別限制,但除了噴塗、輥塗、棒塗、凹版塗覆、模嘴塗覆、刮刀塗覆、噴墨塗覆及刷塗、浸塗等以外,還可使用捲對捲模式塗佈裝置,以連續式進行塗覆。
進而,塗覆液組成物中亦可包含上述以外之添加於塗料之習知材料,例如,亦可包含觸變劑、表面調整劑、消泡劑、調平劑、顏料、染料黏著成分、接著成分、增黏劑等。
作為基材可未特別限制地使用薄膜、不織布、多孔體、板狀體等。
作為構成基材之材料,可舉例乙烯之均聚物或與其他α-烯烴之共聚物、均聚丙烯、丙烯與其他烯烴之共聚物、聚對苯二甲酸乙二酯、聚萘二甲酸乙二酯、聚醯胺醚酮、聚醯亞胺、聚醯胺、聚苯碸、聚苯醚、聚乙烯、聚醚碸、聚醚醚酮、聚苯并咪唑、聚醚醯亞胺、聚醯胺醯亞胺、聚(p-伸苯基-2,6-苯雙噁唑)、氟樹脂、環氧樹脂等之有機樹脂材料,鋁、銅、銀、鐵等之金屬材料,玻璃(氧化矽)、氧化鋁、氧化鎂、氮化鋁、碳化鋁、氮化矽、鈦酸鋇等之無機材料。基材可單獨使用1種,亦可組合2種以上使用。其中,作為基材較佳為聚烯烴,更佳為選自聚乙烯、聚丙烯至少一者、最佳為以聚丙烯/聚乙烯/聚丙烯之依順積層之3層積層體。若使用由此等材料所成之多孔質基材,可作為二次電池用分隔膜使用。多孔基質材為聚烯烴製薄膜之情況,可使用濕式法製造亦可使用乾式法製造而無特別限定。又由3層積層體所成之多孔質基材之情況,較佳3層均以乾式法製造。具有此等構成者,不捲曲,耐熱性、機械強度等良好。
且,乾式法係製造時不使用溶劑之乾式製程,舉例為例如將熔融樹脂以T模嘴熔融成形或噴墨成形等。又,外層及內層可為乾式法亦可為濕式法,濕式法係使用添加・混合有添加物之樹脂製膜為薄膜後,以溶劑萃取添加物之方法。
基材之厚度係全體厚度,根據目的之機械強度、性能、小型化等方面適當選擇,較佳為7.0μm以上,上限較佳為50μm以下。若於該範圍之厚度,則強度高,亦可提高離子傳導性。
又多孔質基材之情況,其透氣度較佳為80s/100cc以上,上限較佳為700s/100cc以下。若具有該範圍之透氣度,則不易短路,離子之移動性亦高。
多孔質基材之孔隙率較佳為30%以上,上限較佳為70%以下。若為該範圍之孔隙率,則機械強度高,亦不產生短路,離子之移動度亦可提高。
多孔質基材之極大孔徑,較佳為0.05μm以上,上限較佳為2μm以下,若於該範圍,則作為分隔膜時,離子之移動性高,電阻亦大幅降低。
塗覆膜之乾燥方法無特別限制,可舉例旋轉乾燥、真空乾燥、溫風乾燥、紅外線乾燥等。乾燥時間亦無特別限制。
構成分隔膜時,可藉由將前述塗覆液組成物塗佈於前述基材表面之方法等構成。
構成電極時,可將前述塗覆液組成物與正極活性物質或負極活性物質混合,並塗佈於前述基材表面或集電體表面之方法,或將混合於正極活性物質或負極活性物質或這二種者塗佈於電極箔,或者將塗覆液組成物薄膜化,並插入正極或負極或這二者之集電體表面可構成電池電極
構成鋰離子二次電池之構件,可大致分為正極電極、負極電極、分隔膜、電解液。正極電極及負極電極分別含有進行電子送出接受之氧化/還原反應之活性物質。正極電極與負極電極係介隔電池用分隔膜而積層之積層構造之電極群及進而可以將其捲取之捲取構造之電極群之形態使用。
作為正極,若為過去已知之鋰離子二次電池所用之正極則無特別限制。正極含有可吸存放出Li+離子之活性物質。
作為負極,若為過去已知之鋰離子二次電池所用之負極則無特別限制。負極含有可吸存放出Li+離子之活性物質。
正極及負極可為介隔電池用分隔膜積層之積層構造的電極群,或進而可以將其捲取之捲取構造之電極群形態使用。作為電解液,可使用將鋰鹽溶解於有機溶劑之溶液。作為鋰鹽,若於溶劑中解離形成Li+離子,於作為電池使用之電壓範圍不引起分解等副反應者則無特別限制。作為有機溶劑,若為能溶解鋰鹽,且於作為電池使用之電壓範圍不引起分解等副反應者則無特別限制。
使用本發明之塗覆液組成物製作之各構件,可適宜使用於前述電池之各構件。
鋰離子電池,除了可用於行動電話、筆記型電腦等之攜帶設備、電動汽車、油電混合式汽車、電動摩托車、電動輔助腳踏車、電動工具、剃刀等之各種機器的電源用途以外,亦可用於過去所知之各種用途。
以下,藉由實施例說明本發明,但本發明不限定於該等實施例。
氧化鋁 昭和電工(股)製AL160SG-3 D50:0.52μm
鱗片狀勃姆石:Serra-Sur(河合石灰工業(股)製)縱橫比:20~40
鱗片狀氧化鋁:Serra-Sur α(河合石灰工業(股)製)縱橫比:20~40
丙烯酸乳液:POLYSOL(註冊商標)LB-350(昭和電工(股)製)
SBR(苯乙烯-丁二烯橡膠):BM400B(日本ZEON(股)製)
聚-N-乙烯基乙醯胺PNVA(註冊商標)-1:GE191-043 (昭和電工(股)製),原始黏度5000mPa・s,固形分4質量%
聚-N-乙烯基乙醯胺PNVA(註冊商標)-2:GE191-104 (昭和電工(股)製),原始黏度18000mPa・s,固形分10質量%
聚-N-乙烯基乙醯胺PNVA(註冊商標)-3:GE191-107 (昭和電工(股)製),原始黏度50mPa・s,固形分10質量%
聚-N-乙烯基乙醯胺PNVA(註冊商標)-4(N-乙烯基乙醯胺與丙烯酸鈉(共聚合比=90:10(莫耳比))之共聚物):GE167-103(昭和電工(股)製),原始黏度5000mPa・s,固形分10質量%
羧甲基纖維素 CMC-Na:MAC350HC(日本製紙(股)製)
聚乙烯吡咯啶酮:PVP K-90(東京化成工業(股)製)
・分散劑
聚丙烯酸銨:Aron(註冊商標) A-30SL(東亞合成(股)製)
十二烷基苯磺酸鈉:NEOPELEX(註冊商標) G-65(花王(股)製)
[實施例1~10,比較例1~10]
於200ml樹脂容器中將離子交換水、分散劑、黏合劑、增黏劑、填料依序計量表1記載之規定量,投入自轉公轉型混練機(THINKY公司製:ARE-250)。密封,以混合(MIXING)60秒及脫泡(Defoaming)60秒之條件混合而獲得均勻之塗覆液組成物。
且分散劑、黏合劑、增黏劑係固形分之質量份。
針對所得之塗覆液組成物進行以下評價。
以養護帶固定作為基材的厚度16μm之聚丙烯薄片,進而以雙面膠帶將聚丙烯薄片固定搭載於塗覆機之塗覆台(15cm×30cm:厚度0.1μm),使用棒塗機(YOSHIMITSU精機股份有限公司製 寬:50mm×厚度:5μm)以自動塗覆機(TESTER產業股份有限公司製Pi-1210)以200mm/秒之速度塗覆所得之塗覆液組成物3.5g。
隨後,以溫風乾燥器以40℃溫度將塗覆之聚丙烯薄片乾燥1小時,製作塗覆膜。
使用Brookfield公司製DV2T型黏度計Spindle SC4-28附水夾套之少量樣本轉換器,於樣本固持器中放入塗覆液組成物20g,於0.3rpm、100rpm之剪切速度測定剪切黏度。
以Brookfield公司製DV2T型黏度計Spindle SC4-28附水夾套之少量樣本轉換器,於50rpm評價塗覆液組成物於23℃之黏度。
TI值(搖變性指數)係以下述式算出。
TI值=於0.01/s之低剪切速度之黏度(Pa・s)÷於10000/s之高剪切速度之黏度(Pa・s)
使用AntonParr製旋轉式黏度計(流變儀)測定。具體而言於23℃之黏度係自剪切速度0.01sec
-1至10000sec
-1,歷時400秒提高速度同時測定,連續自10000sec
-1至0.01sec
-1歷時400秒降低速度同時測定。將剪切速度降低同時測定時之測定值作為各剪切速度下之黏度,求出表2所示之剪切速度下之黏度的比率。
<塗覆膜厚度>
使用TECLOCK公司製定壓厚度測定器PF-11J,依照JISK6400-1-2004測定塗覆膜之中心及自中心上下遠離10cm之2點,共計3點並進行加權平均。
<外觀>
藉以下基準實施塗覆膜之表面外觀判定。
○:於塗覆表面未確認到空隙。
△:於塗覆表面確認到10個以內之空隙。
×:於塗覆表面確認到超過10個空隙。
<表面粗糙度比>
使用滑行式之Surtronic-Duo表面粗糙度計(TAYLOR HOBSON公 司製),依照JIS B0601-2013測定於塗覆膜中心及自中心上下遠離10cm之2點,共計3點表面粗糙度Ra並予以平均。以Ra除以塗覆膜厚作為表面粗糙度比。
<剝離>
對塗覆膜之印刷面(與基材相反側之面)藉由
NICHIBAN製15mm寬賽璐吩膠帶進行賽璐吩膠帶剝離試驗,並藉以下3階段評價塗覆膜與聚丙烯薄片間之密著性。
○:塗覆部分未剝離。
△:塗覆部分有剝離。
×:塗覆部分於試驗前即剝離。
<收縮率>
將塗覆膜之塗覆方向設為M方向、與其垂直之方向設為T方向,以各邊於M方向、T方向一致之方式切出1cm見方之正方形樣品,分別放入調節至內溫150℃及200℃之氣炸鍋中於大氣下加熱15分鐘,對於M方向(塗覆之方向)及T方向(對於塗覆方向垂直之方向)各者,以百分比表示收縮至熱處理後長度(l)相對於熱處理前長度(L)之比例。
各方向之收縮率(%) = (L-1)/L×100
M方向、T方向之收縮率之算術平均作為收縮率。
實施例6及比較例9之斜線部分之項目係無法算出。又實施例10之斜線部分係未測定。超過表示測定界限以上。
根據表2可知,實施例之塗覆膜,表面粗糙度比均為0.178以下,獲得平滑表面。另一方面比較例之塗覆膜,表面粗糙度比均為0.200以上,表面並非平滑。
根據表2,實施例之塗覆膜,於200℃之收縮率為18.58%以下。另一方面比較例之收縮率,於200℃之收縮率為20.60%以上,且如圖2所示塗覆膜之形狀潰散無法測定尺寸,不適合高溫時。
根據表2,於實施例之塗覆膜,表面外觀均未確認到空隙。另一方面比較例之塗覆膜均確認到空隙。
針對實施例4、比較例7及8,進行耐熱試驗前之塗覆膜之狀況觀察。
耐熱試驗前之附塗覆膜薄片之狀況觀察示於圖1,於200℃加熱之附塗覆膜薄片之狀況觀察示於圖2。於比較例7、8於塗覆膜產生破裂及剝離,但實施例4則無變化。
[圖1]顯示耐熱試驗前之實施例7、比較例7及8之塗覆膜之光學照片。
[圖2]顯示耐熱試驗後之實施例7、比較例7及8之塗覆膜之光學照片。
Claims (12)
- 一種塗覆液組成物,其特徵係包含填料、溶劑、分散劑、增黏劑、黏合劑,塗覆於基材形成0.5~20μm厚之塗覆膜時,塗覆膜於200℃、15分鐘之收縮率為20.0%以下,其中,黏合劑相對於填料100質量份為1質量份以上30質量份以下,分散劑相對於填料100質量份為0.1質量份以上5質量份以下,塗覆液組成物中之填料之質量為20~70質量%,增黏劑與填料之質量比(填料/增黏劑)為0.1以上200以下,相對於溶劑100質量份,填料為0.1~200質量份,前述黏合劑係選自丙烯酸乳液、苯乙烯-丁二烯聚合物乳液之乳液,前述填料為氧化鋁,前述增黏劑之黏度以原始黏度計為5000mPa.s以上10000mPa.s以下。
- 如請求項1之塗覆液組成物,其中前述增黏劑係聚N-乙烯基羧醯胺。
- 如請求項2之塗覆液組成物,其中前述增黏劑係聚N-乙烯基乙醯胺。
- 如請求項1之塗覆液組成物,其中前述溶劑為水。
- 如請求項1之塗覆液組成物,其中前述基材係聚烯烴製薄膜。
- 如請求項5之塗覆液組成物,其中前述聚烯烴製薄膜係選自聚乙烯、聚丙烯之至少一者。
- 如請求項5之塗覆液組成物,其中前述聚烯烴製薄膜係聚丙烯、聚乙烯、聚丙烯之3層積層薄膜。
- 一種附塗覆膜之基材,其係包含由如請求項1至7中任一項之塗覆液組成物形成之塗覆膜及基材。
- 一種分隔膜,其係由如請求項8之附塗覆膜之基材所成。
- 一種二次電池,其係使用如請求項9之分隔膜。
- 一種鋰離子二次電池,其係使用如請求項9之分隔膜。
- 一種電極材料,其係於基材表面具備由如請求項1至7中任一項之塗覆液組成物形成之塗覆膜。
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TW201412384A (zh) * | 2012-08-23 | 2014-04-01 | Jnc Corp | 耐熱性優良的複合多孔質膜 |
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