TWI591880B - 隔板之製法，由彼製成的隔板以及含此隔板的電化學裝置 - Google Patents

隔板之製法，由彼製成的隔板以及含此隔板的電化學裝置 Download PDF

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TWI591880B
TWI591880B TW104110819A TW104110819A TWI591880B TW I591880 B TWI591880 B TW I591880B TW 104110819 A TW104110819 A TW 104110819A TW 104110819 A TW104110819 A TW 104110819A TW I591880 B TWI591880 B TW I591880B
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inorganic particles
separator
separator according
lithium
coating
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TW201601368A (zh
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李柱成
陳善美
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Ｌｇ化學股份有限公司
東麗電池隔膜有限公司
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Description

隔板之製法，由彼製成的隔板以及含此隔板的電化學裝置
本發明揭示內容有關一種諸如鋰二次電池之電化學裝置的隔板之製法，由彼形成之隔板及含此隔板之電化學裝置。
本案主張2014年4月1日在大韓民國申請之韓國專利申請案編號10-2014-0038729的優先權，其揭示內容係以引用方式併入本文。
最近，對於能量儲存技術的重視日漸增長。隨著能量儲存技術之應用領域擴展到行動電話、錄相機、膝上型電腦及甚至是電動車，愈來愈努力研發電化學裝置。就此言之，電化學裝置已吸引了大部分的注意力，其中，發展可再充電之二次電池為特別引人注意的焦點。近年來，徹底研究及發展新穎電極及電池設計以改善電池的電容密度及比能量。
在現存二次電池中，1990年代早期所發展之鋰二次 電池在與使用電解質水溶液之傳統電池(諸如Ni-MH電池，Ni-Cd電池及H2SO4-Pb電池)比較下，因為其操作電壓較高及遠高出許多的能量密度而受到許多注意。然而，該等鋰離子電池具有因為使用有機電解質溶液而造成與安全性相關的問題之缺點，例如點燃及爆炸，且製程複雜。設計來克服鋰離子電池之弱點的鋰離子聚合物二次電池被陳述成下一代電池中之一，但其容量仍低於鋰離子電池，且放電容量--尤其是在低溫下之放電容量--不足，是故，亟需改良。
有許多公司生產該等電化學裝置，但其安全性特徵顯示彼此不同的面相。評估且確定電化學裝置之安全性極為重要。最重要的顧慮中之一是電化學裝置在故障時應不會對使用者造成傷害，針對此項目的，安全性標準對於電化學裝置的點燃及爆炸加以嚴格之規定。在電化學裝置的安全性特徵中，在電化學裝置過熱或熱失控或隔板穿孔時，該電化學裝置爆炸的風險極高。尤其，一般用為電化學裝置的隔板之以聚烯烴為主的多孔性聚合物基板在高於或等於100℃的溫度時因為材料特徵及程序特徵(包括拉伸)顯示出嚴重的熱收縮，造成正極(或陰極)與負極(或陽極)之間的短路。
為解決電化學裝置之安全性問題，有建議隔板要具有多孔性有機-無機塗層，該塗層是藉由過量無機顆粒及黏合劑聚合物的混合物塗覆於具有複數個孔的多孔性聚合物基板之至少一表面而形成。該多孔性有機-無機塗層中所 包括的無機顆粒具有良好耐熱性，藉以防止在電化學裝置過熱時，正極(或陰極)與負極(或陽極)之間的短路。
通常，具有多孔性有機-無機塗層的隔板是經由藉浸塗法在多孔性聚合物基板上形成有機-無機塗層的方法製得。然而，因為使用以有機溶劑為主之漿液，故此製造方法在製造電化學裝置時，具有安全性風險，且較不環保及較不具經濟效益。
與以有機溶劑為主之漿液相對的，水性漿液安全、環保且經濟效益高，但其表面張力高造成在以聚烯烴為主的基板上的潤濕性低之問題，限制了在隔板塗覆時的用途。
因此，本發明揭示內容之目的就是要提出一種製備隔板的方法，藉由該方法經由將漿液塗覆於多孔性聚合物基板上的製程，製得具有機-無機複合多孔性塗層的隔板，在此情況下，使用具有預定性質的水性漿液來改善該多孔性聚合物基材的潤濕性。
本發明揭示內容的另一目的是提供藉由該製備方法所製得的隔板。
本發明揭示內容之再另一目的是提供一種具有隔板的電化學裝置。
為達成前述目的，本發明揭示內容提供一種製備隔板的方法，其包括製備包括無機顆粒、黏合劑聚合物及水性介質的水性漿液，將該水性漿液塗覆於多孔聚合物基板的至少一表面上，以形成有機-無機複合多孔性塗層，其中該水性漿液之毛細數為0.3至65，毛細數是由下式1決定：<式1>毛細數(Ca)=(μ×U)/σ
其中μ=黏度(kgf．s/m2)，U=塗覆速度(m/s)，且σ=表面張力(kgf/m)。
根據具體實施態樣，提供一種藉該製備方法製得的隔板。
根據具體實施態樣，提供一種電化學裝置，其包括正極(或陰極)、負極(或陽極)、及插置於該正極(或陰極)與該負極(或陽極)之間的隔板。
根據例示之執行狀況，該電化學裝置可為鋰二次電池。
本發明揭示內容藉由提供一種製備隔板的方法而確保製程之安全性及經濟效率，該方法是使用水性漿液在多孔性聚合物基板表面形成有機-無機複合塗層，且可使用前述製得之隔板來改善電化學裝置的安全性。
下文中，詳細描述本發明揭示內容。在描述之前，應瞭解說明書及所附申請專利範圍中所使用之術語皆不應視為受限於一般及字典含義，而應基於發明者針對最佳說明所容許適當定義術語的原理，而對應於本發明技術態樣之意義及觀念作出闡釋。
本發明之一具體實施態樣之製備隔板的方法是包括製備包含有無機顆粒、黏合劑聚合物及水性介質的水性漿液，將該水性漿液塗覆於多孔性聚合物基板的至少一表面上，形成有機-無機複合多孔性塗層。
該水性漿液的毛細數可藉下式1決定：<式1>毛細數(Ca)=(μ×U)/σ
其中μ表示黏度(kgf．s/m2)，U表示塗覆速度(m/s)，且σ表示表面張力(kgf/m)。
毛細數為用以決定水性漿液之潤濕能力的因數，藉由適當的控制此因數，可達到水性漿液於多孔性聚合物基板上的潤濕，可幫助塗覆。
毛細數是由水性漿液的黏度、塗覆速度及表面張力決定，且黏度可基於水性漿液之固體含量及供應溫度而改變。塗覆速度代表將水性漿液塗覆於基板上時的速度，基於塗覆速度，可改變水性漿液於基板上的潤濕。當具有低值表面張力時，達到潤濕，使其較有利於施加漿液，且此值可經由添加劑而達到最小。
為經由毛細數確定水性漿液之最佳潤濕能力，由前式1所決定之值可具有介於0.3及65之間的範圍，例如，介於0.5及45之間。在此範圍內，可在低表面張力下達到對多孔性聚合物基材之潤濕，可幫助塗覆。
水性漿液的黏度可調整至最佳範圍，且在此情況下，可使用稠化劑。稠化劑若可調整水性漿液的黏度則不限於特定類型，但可包括例如羧甲基纖維素、甲基纖維素、羥基甲基纖維素、乙基纖維素、聚乙烯醇、氧化澱粉、磷醯化澱粉、酪蛋白及其鹽。此等例示稠化劑是單獨或於任何比例下組合使用。當使用稠化劑時，稠化劑相對於水性漿液的比例通常相對於無機物為0.1質量%或更高，較佳為0.5質量%或更高，更佳為0.6質量%或更高，且上限通常為5質量%或更低，較佳為3質量%或更低，更佳為2質量%或更低。當該比例低於此範圍時，塗料經常明顯的減少。當比例高於此範圍時，易降低該等無機顆粒或黏合劑在漿液中之含量。
水性漿液之黏度可視供料溫度而改變，黏度隨著溫度降低而增高且隨著溫度升高而降低。因此，藉由選擇最佳供料溫度，可適當地控制水性漿液的黏度。供料溫度範圍可為例如10℃至50℃。
水性漿液經稠化劑調整之黏度可具有介於0.005kgf．s/m2及0.05kgf．s/m2之間的範圍，例如，介於0.01kgf．s/m2及0.25kgf．s/m2之間。
水性漿液之塗覆速度可適當的調整至水性漿液可輕易 塗覆於多孔性聚合物基材上的範圍，即，確保潤濕能力的範圍。塗覆速度可藉由製程中(例如)諸如滾筒速度或張力變數之機械控制而決定，且可具有介於10m/s及100m/s之間的範圍，例如介於30m/s及70m/s之間。當塗覆速度超過該範圍時，經濟效率因為水性漿液塗覆之降低或製程時間拉長而降低。
水性漿液之表面張力為確定在低表面能下對多孔性聚合物基材的潤濕能力的重要因子，較佳是賦予儘可能低的表面張力。為達此目的，將添加劑導至水性漿液內可引發表面張力降低，該添加劑可包括乳化劑，明確的說，為親水性界面活性劑，例如至少一種選自由聚氧乙烯(10)-氫化蓖麻油、聚氧乙烯(40)-氫化蓖麻油、聚氧乙烯(60)-氫化蓖麻油、矽氧烷、聚山梨酯60、聚山梨酯80、及聚山梨酯20所組成之群組的親水性界面活性劑。該添加劑可添加含量為該水性漿液的重量之約0.1wt%至約3.0wt%。
該水性漿液的表面張力可經由添加劑調至介於0.0015kgf/m及0.007kgf/m之間的範圍內。
該水性漿液中所使用的水性介質可為水或醇與水之混合物。該醇可包括但不限於甲醇、乙醇、丙醇、異丙醇、丁醇、第三丁醇及戊醇。
待使用水性漿液塗覆之多孔性聚合物基材可為多孔性聚合物基材或多孔性聚合物不織布基材。
作為多孔性聚合物膜基材，如眾所周知，可使用由諸 如聚乙烯及聚丙烯之聚烯烴的多孔性聚合物膜製得的隔板，且聚烯烴多孔性聚合物基材在例如介於80℃及130℃之間的溫度展現關閉之功能。聚烯烴多孔性聚合物膜可製自以聚烯烴-為主之聚合物，其包括單獨使用或組合使用之聚乙烯諸如高密度聚乙烯、直鏈低密度聚乙烯、低密度聚乙烯及超高分子量聚乙烯、聚丙烯、聚丁烯及聚戊烯。而且，該多孔性聚合物膜基材可使用各種聚合物製造，其包括聚酯，以及聚烯烴。而且，該多孔性聚合物膜基材可形成為至少兩膜層的堆疊結構，膜層各可由前述例如聚烯烴及聚酯的聚合物單獨或組合地形成。
該多孔性聚合物不織布基材可使用聚合物自纖維製得，該等聚合物包括前述以聚烯烴-為主之聚合物或其他具有耐熱性之聚合物，例如聚酯，諸如聚對苯二甲酸伸乙酯(PET)。相同地，該多孔性聚合物不織布基材可自纖維單獨或組合地製得。
該多孔性聚合物膜基材的材料或形狀可基於所期望之目的而變化性的選擇。
多孔性聚合物基材之厚度無特別限制，但較佳厚度為1μm至100μm範圍內，更佳為5μm至50μm，且對多孔性聚合物基材之孔徑及孔隙度無特別限制，但孔徑及孔隙度個別較佳為0.01μm至50μm及10%至95%。
將水性漿液塗覆於多孔性聚合物基材上的方法不特別限制，但較佳是使用狹縫式塗覆方法或浸塗法。狹縫式塗覆是一種塗覆方法，將經由縫模供應的塗覆溶液塗覆在基 材的前表面上，基於自定量泵供應的流速來控制多孔性塗層的厚度。浸塗法為一種塗覆方法，將基材浸泡於裝有塗覆溶液的槽中，多孔性塗層之厚度可基於該塗覆溶液之濃度及自該塗覆溶液槽取出基材的速度來控制，更精確的厚度控制是在浸泡後經由Mayer刮棒後調節來達成，之後，在烘箱中乾燥，形成位在多孔性聚合物基材之兩表面上的塗層。
在其中將無機顆粒分散於水性溶劑中且將黏合劑聚合物溶解或分散於該水性溶劑中的漿液中，該等無機顆粒不特別限制，只要其係電化學安定性。即，本發明揭示內容之有效無機顆粒不限於特別類型，只要其在電化學裝置應用的操作電壓範圍(例如，Li/Li+為0至5V)中不造成氧化及/或還原反應。尤其，當使用具有高介電常數的無機顆粒作為無機顆粒時，該等無機顆粒可促使電解質鹽(例如鋰鹽)在液體電解質中的溶解度增高，且可改善電解質溶液的離子傳導性。
因前述因素，該等無機顆粒以包括具有大於或等於5之高介電常數的無機顆粒為佳，更佳是大於或等於10。該等具有大於等於5之介電常數的無機顆粒包括作為非限制實例的BaTiO3、Pb(Zr,Ti)O3(PZT)、Pb1-xLaxZr1-yTiyO3(PLZT,0<x<1,0<y<1)、Pb(Mg1/3Nb2/3)O3-PbTiO3(PMN-PT)、氧化鉿(HfO2)、SrTiO3、SnO2、CeO2、MgO、NiO、CaO、ZnO、ZrO2、Y2O3、Al2O3、水鋁土(γ-AlO(OH))、TiO2、SiC或其混合 物。
而且，該等無機顆粒可包括能輸送鋰離子的無機顆粒，即含有鋰原子且具有在不儲存鋰的情況下傳輸鋰離子的功能之無機粒子。該等可輸送鋰離子的無機顆粒包括作為非限制實例之磷酸鋰(Li3PO4)、磷酸鈦鋰(LixTiy(PO4)3,0<x<2,0<y<3)、磷酸鈦鋁鋰(LixAlyTiz(PO4)3,0<x<2,0<y<1,0<z<3)、(LiAlTiP)xOy為主之玻璃(0<x<4,0<y<13)諸如14Li2O-9Al2O3-38TiO2-39P2O5、鈦酸鑭鋰(LixLayTiO3,0<x<2,0<y<3)、硫代磷酸鍺鋰(LixGeyPzSw,0<x<4,0<y<1,0<z<1,0<w<5)諸如Li3.25Ge0.25P0.75S4、氮化鋰(LixNy,0<x<4,0<y<2)諸如Li03N,SiS2為主之玻璃(LixSiySz,0<x<3,0<y<2,0<z<4)諸如Li3PO4-Li2S-SiS2、P2S5為主之玻璃(LixPySz,0<x<3,0<y<3,0<z<7)諸如LiI-Li2S-P2S5或其混合物。
而且，該等無機顆粒之平均晶粒徑不特別限制，但用以形成具有均勻厚度及適當之孔隙度的多孔性塗層時，期望是介於0.001μm及10μm之間的範圍內。當平均晶粒徑小於0.001μm時，可能破壞分散性，當平均晶粒徑大於10μm時，該多孔性塗層之厚度可能會增加。
作為黏合劑聚合物，較佳使用玻璃轉化溫度(Tg)介於-200℃及200℃之間的聚合物，其可改善最後將形成之多孔性塗層的機械性質，諸如可撓性及彈性。
而且，黏合劑聚合物並非必需具有離子傳導能力，但當使用具有離子傳導能力的聚合物時，可進一步改善電化學裝置之性能。是故，具有儘可能高之介電常數的黏合劑聚合物較佳。實際上，因為鹽在電解質溶液中之解離程度視電解質溶劑之介電常數而定，隨著黏合劑聚合物之介電常數的增加，鹽於電解質中之解離程度可得到改善。黏合劑聚合物之介電常數可在1.0至100(在1kHz頻率下測得)範圍內，尤其以大於等於10較佳。
黏合劑聚合物可包括作為非限制實例之以苯乙烯-丁二烯橡膠(SBR)-為主之聚合物及以丙烯酸酯為主之聚合物。
該等無機顆粒與黏合劑聚合物的重量比較佳於例如介於50：50及99：1之間的範圍內，更佳係介於60：40及99：1之間，再更佳係介於70：30及95：5之間。當該等無機顆粒對黏合劑聚合物之含量比低於50：50時，因為聚合物含量高，故所形成之多孔性塗層的孔徑及孔隙度可降低。當該等無機顆粒之含量高於99重量份時，因為黏合劑聚合物含量低，故所形成之多孔性塗層之抗剝離性可能降低。
乳液態之黏合劑聚合物可分散於溶劑中，為幫助均勻混合及溶劑移除，可用溶劑之非限制實例可包括水、甲醇、乙醇、異丙醇或其混合物。
其中該等無機顆粒分散於溶劑中且黏合劑聚合物溶於溶劑中的漿液可藉著將黏合劑聚合物溶解於溶劑且添加並分散該等無機顆粒而製備。該等無機顆粒可在粉碎至最佳 尺寸後添加，但較佳是將該等無機顆粒添加至黏合劑聚合物之溶液中，之後在使用球磨方法粉碎之情況下將該等無機顆粒分散。
藉前述方法製得之有機-無機複合多孔性塗層可在多孔性聚合物基材上之潤濕性及後續黏結性上得到改良。在有機-無機複合多孔性塗層中，當該等無機顆粒堆積且彼此接觸時，該等無機顆粒藉黏合劑聚合物而彼此黏結，而形成位在該等無機顆粒之間的隙間體積，而位在該等無機顆粒之間的隙間體積變成空隙形成微孔。
即，黏合劑聚合物使得該等無機顆粒彼此黏著以保持顆粒的黏合狀態，例如，黏合劑聚合物連結且撐住該等無機顆粒。而且，有機-無機複合多孔性塗層之微孔的形成具有界定空隙而位在該等無機顆粒之間的隙間體積，且此係由該等無機顆粒之密合堆積或緊密堆積結構中實質表面接觸的無機顆粒所界定的空間。
電化學裝置可藉由層積正極(或陰極)及負極(或陽極)與藉夾置於其間而由前述方法製備之隔板製得。電化學裝置是包括所有促進電化學反應的裝置，例如，所有類型的一次及二次電池、燃料電池、太陽能電池及電容器諸如超級電容。尤其，在二次電池中，期望有鋰二次電池，包括鋰金屬二次電池、鋰離子二次電池、鋰聚合物二次電池或鋰離子聚合物二次電池。
要與本發明揭示內容之隔板一起應用的電極無特別限制，電極可依藉技術界已知之一般方法將電極活性材料黏 合於電極集流器之方式製得。在電極活性材料中，正極(或陰極)活性材料之非限制實例包括一般可使用於電化學裝置的正極(或陰極)之通用型正極(或陰極)活性材料，特佳為鋰化氧化錳、鋰化氧化鈷、鋰化氧化鎳、鋰化氧化鐵或其複合氧化物。負極(或陽極)活性材料之非限制實例包括一般可使用於電化學裝置的負極(或陽極)之通用型負極(或陽極)活性材料，尤其較佳為鋰金屬或鋰合金，及鋰吸附材料諸如碳、石油焦、石墨及其他碳。正極(或陰極)集流器是由作為非限制實例之以鋁、鎳或其組合為主的薄箔製得，而負極(或陽極)集流器是由作為非限制實例之以銅、金、鎳、銅合金或其組合物為主的薄箔製得。
可使用於本發明揭示內容之電化學裝置的電解質可為其中鹽溶解或解離於有機溶劑中的電解質溶液，該鹽具有由例如下所示之結構：A+B-，其中A+為鹼金屬陽離子，諸如Li+、Na+、K+、或其組合物且B-為陰離子，如PF6 -、BF4 -、Cl-、Br-、I-、ClO4 -、AsF6 -、CH3CO2 -、CF3SO3 -、N(CF3SO2)2 -、C(CF2SO2)3 -、或其組合物，且有機溶劑包括但不限於碳酸丙二酯(PC)、碳酸乙二酯(EC)、碳酸二乙酯(DEC)、碳酸二甲酯(DMC)、碳酸二丙酯(DPC)、二甲基亞碸、乙腈、二甲氧基乙烷、二乙氧基乙烷、四氫呋喃、N-甲基-2-吡咯啶酮(NMP)、碳酸乙酯甲酯(EMC)γ-丁內酯或其混合物。
電解質溶液之傾注可基於製造方法及最終產物所需之 物性而在電池製程中的任何適當步驟中執行。即，電解質溶液之傾注可在電池組裝前或在電池組裝的最終步驟中施加。
下文中，經由用以幫助理解的實施例來描述本發明揭示內容。然而，本發明揭示內容可採用各種其他形式，本發明揭示範圍不應解釋為受限於以下實施例。本發明揭示之實施例係用以向一般熟悉與本發明揭示相關的技術之技術人員更充分的說明本發明揭示內容。
實施例1
作為無機物而粒徑500nm的水鋁土(γ-AlO(OH))(Nabaltec Apyral AOH60)、作為黏合劑聚合物之苯乙烯-丁二烯橡膠(SBR)(JSR TRD102A)及作為稠化劑之羧基甲基纖維素(CMC)(Daicel Chemical Industry 1220)在90：6：4比例下混合，在50℃溶於水中歷經約3小時或更久，之後使用球磨方法將無機顆粒粉碎且分散於其中歷經12小時或更久，製備含有30%水準的固體之水性漿液。為降低所製備漿液的表面張力，添加對應於漿液重量為0.1%之量的乳化劑(道康寧67添加劑)。所製備漿液的黏度為0.007kgf．s/m2，且表面張力為0.0025kgf/m。
藉縫模法於0.2m/sec速度下將漿液塗覆於12μm厚多孔膜上(SK innovation 512GK)，使漿液通經溫度調整至80℃的烘箱以將漿液中所包括的溶劑乾燥，製得具有調整至4μm之厚度的多孔性塗層的隔板。在前述條件 下，毛細數為0.56。形成之隔板達到均勻厚度，寬度方向可有1μm或更小的偏差。
實施例2
藉由執行如同實施例1之方法來製得漿液及隔板，不同處是塗覆速度變成1.5m/sec。在前述條件下，毛細數為4.2，形成之隔板達到均勻厚度，寬度方向可有1μm或更小的偏差。
實施例3
藉由執行如同實施例1之方法來製得漿液及隔板，不同處是漿液組成變成85：10：5。在前述條件下，毛細數為24.0，形成之隔板達到均勻厚度，寬度方向可有1μm或更小的偏差。
對照例1
藉由執行如同實施例1之方法來製得漿液及隔板，不同處是不使用乳化劑。在前述條件下，毛細數為0.23。塗覆製程中發生小溪現象，結果，無法在基材的整個寬度上形成均勻之多孔性塗層。

Claims (16)

  1. 一種製備隔板的方法，其包含：製備包含無機顆粒、黏合劑聚合物及水性介質之水性漿液；及將該水性漿液塗覆於多孔性聚合物基材的至少一表面上，形成有機-無機複合物多孔性塗層，其中該水性漿液之毛細數為0.3至65，毛細數是由下式1決定：毛細數(Ca)=(μ×U)/σ其中μ=黏度(kgf．s/m2)，U=塗覆速度(m/s)，且σ=表面張力(kgf/m)，其中該黏度(kgf．s/m2)μ係為0.005至0.05，其中塗覆速度(m/s)U係為0.15至2.0，其中該表面張力(kgf/m)σ係自0.0015至0.005，其中該有機-無機複合物多孔性塗層的形成是藉狹縫式塗覆方法或浸塗法執行。
  2. 如申請專利範圍第1項之製備隔板的方法，其中毛細數Ca係為0.4至45。
  3. 如申請專利範圍第1項之製備隔板的方法，其中該水性介質為水或醇與水之混合物。
  4. 如申請專利範圍第1項之製備隔板的方法，其中多孔性聚合物基材為多孔性聚合物膜基材或多孔性聚合物不織布基材。
  5. 如申請專利範圍第4項之製備隔板的方法，其中 該多孔性聚合物膜基材為以聚烯烴為主之多孔性聚合物膜基材。
  6. 如申請專利範圍第5項之製備隔板的方法，其中該以聚烯烴為主之多孔性聚合物膜基材係自至少一種選自由聚乙烯、聚丙烯、聚丁烯、及聚戊烯所組成之群組的聚合物形成。
  7. 如申請專利範圍第1項之製備隔板的方法，其中該多孔性聚合物基材之厚度係為5μm至50μm，且孔徑及孔隙度係個別為0.01μm至50μm及10%至95%。
  8. 如申請專利範圍第1項之製備隔板的方法，其中該無機顆粒的平均晶粒大小為0.001μm至10μm。
  9. 如申請專利範圍第1項之製備隔板的方法，其中該等無機顆粒為選自由具有大於或等於5之高介電常數之無機顆粒、可輸送鋰離子之無機顆粒及其混合物所組成之群組的無機顆粒。
  10. 如申請專利範圍第9項之製備隔板的方法，其中該等具有大於或等於5之高介電常數之無機顆粒為選自由以下各者組成之群組的任一者之無機顆粒：BaTiO3、Pb(Zr,Ti)O3(PZT)、Pb1-xLaxZr1-yTiyO3(PLZT,0<x<1,0<y<1)、Pb(Mg1/3Nb2/3)O3-PbTiO3(PMN-PT)、氧化鉿(HfO2)、SrTiO3、SnO2、CeO2、MgO、NiO、CaO、ZnO、ZrO2、SiO2、Y2O3、Al2O3、水鋁土(γ-AlO(OH))、SiC及TiO2或其混合物。
  11. 如申請專利範圍第9項之製備隔板的方法，其中 該等可輸送鋰離子的無機顆粒為選自由以下各者組成之群組的任一者之無機顆粒：磷酸鋰(Li3PO4)、磷酸鈦鋰(LixTiy(PO4)3、0<x<2,0<y<3)、磷酸鈦鋁鋰(LixAlyTiz(PO4)3,0<x<2,0<y<1,0<z<3)、以(LiAlTiP)xOy為主之玻璃(0<x<4,0<y<13)、鈦酸鑭鋰(LixLayTiO3,0<x<2,0<y<3)、硫代磷酸鍺鋰(LixGeyPzSw,0<x<4,0<y<1,0<z<1,0<w<5)、氮化鋰(LixNy,0<x<4,0<y<2)、以SiS2(LixSiySz,0<x<3,0<y<2,0<z<4)為主之玻璃、及P2S5(LixPySz,0<x<3,0<y<3,0<z<7)為主之玻璃或其混合物。
  12. 如申請專利範圍第1項之製備隔板的方法，其中該等無機顆粒與該黏合劑聚合物之重量比是在介於50：50及99：1之間的範圍內。
  13. 如申請專利範圍第1項之製備隔板的方法，其中該黏合劑聚合物係為選自由以苯乙烯-丁二烯橡膠(SBR)-為主之聚合物及以丙烯酸酯為主之聚合物或其混合物所組成之群組的任一者。
  14. 一種藉由如申請專利範圍第1至13項中任一項之製備方法製得的隔板。
  15. 一種電化學裝置，其包含正極、負極及插置於該正極與負極之間的如申請專利範圍第14項之隔板。
  16. 如申請專利範圍第15項之電化學裝置，其中該電化學裝置為鋰二次電池。
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KR101369326B1 (ko) 2011-12-27 2014-03-04 주식회사 엘지화학 세퍼레이터의 제조방법 및 이에 따라 제조된 세퍼레이터를 구비한 전기화학소자
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CN103000848B (zh) * 2012-11-29 2016-09-07 东莞新能源科技有限公司 复合多孔性隔膜及其制备方法
CN103311486B (zh) * 2013-05-14 2016-06-08 中南大学 一种有机-无机复合隔膜及其制备和应用
CN103441230B (zh) * 2013-08-21 2016-03-09 东莞新能源科技有限公司 有机/无机复合多孔隔离膜及其制备方法及电化学装置

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US20160226051A1 (en) 2016-08-04
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EP3043403A1 (en) 2016-07-13
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