CN105814711B - 隔膜的制造方法、由该方法制造的隔膜以及包含隔膜的电化学装置 - Google Patents

隔膜的制造方法、由该方法制造的隔膜以及包含隔膜的电化学装置 Download PDF

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CN105814711B
CN105814711B CN201580003015.6A CN201580003015A CN105814711B CN 105814711 B CN105814711 B CN 105814711B CN 201580003015 A CN201580003015 A CN 201580003015A CN 105814711 B CN105814711 B CN 105814711B
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manufacturing
diaphragm
inorganic particulate
diaphragm according
coating
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CN105814711A (zh
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李柱成
陈善美
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Toray Industries Inc
LG Energy Solution Ltd
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Toray Industries Inc
LG Chemical Co Ltd
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Abstract

本发明的隔膜的制造方法包括以下步骤：准备包含无机粒子、粘合剂聚合物和水性材料的水性浆料；以及将所述水性浆料涂布在多孔聚合物基材的至少一个表面上，以形成有机‑无机复合多孔涂层，其中所述水性浆料的毛细管数在0.3至65的范围内。

Description

隔膜的制造方法、由该方法制造的隔膜以及包含隔膜的电化 学装置
技术领域
本发明涉及一种诸如锂二次电池的电化学装置的隔膜的制造方法、由该方法形成的隔膜及包含所述隔膜的电化学装置。
本申请要求2014年4月1日在韩国提交的韩国专利申请号10-2014-0038729的优先权，以引用的方式将其公开内容并入本文中。
背景技术
近来，对于能量储存技术的兴趣日渐增长。随着能量储存技术的应用领域扩展到移动电话、便携式摄像机、膝上型电脑以及甚至是电动车，越来越努力研发电化学装置。在这一方面，电化学装置受到了最多关注，其中，可再充电的二次电池的发展为特别引人注意的焦点。近年来，正在对新型电极和电池设计进行深入研究和开发以改善电池的容量密度和比能量。
在现存的二次电池中，九十年代早期所发展的锂二次电池因为比使用水性电解液的传统电池(诸如Ni-MH电池，Ni-Cd电池及H2SO4-Pb电池)具有更高的操作电压和远高出许多的能量密度的优点而受到大量关注。然而，这种锂离子电池具有因为使用有机电解液而造成的与安全性相关的问题的缺点，例如点燃及爆炸，且制造复杂。设计为克服锂离子电池的弱点的锂离子聚合物二次电池被描述为下一代电池中的一种，但其容量仍低于锂离子电池的容量，且放电容量、尤其是在低温下的放电容量不足，因此对改善存在迫切的需求。
有许多公司生产这种电化学装置，但其安全特性显示彼此不同的方面。评估和确保电化学装置的安全性是极为重要的。最重要的考量之一是电化学装置在故障时应不会对使用者造成伤害，为此，安全性标准对于电化学装置的点燃及爆炸加以严格规定。在电化学装置的安全特性中，在电化学装置过热或热失控或隔膜穿孔时，该电化学装置爆炸的风险极高。特别地，通常用作电化学装置的隔膜的聚烯烃基多孔聚合物基材在高于或等于100℃的温度下因为材料特征及程序特征(包括拉伸)而显示严重的热收缩行为，造成正极(或阴极)与负极(或阳极)之间的短路。
为解决电化学装置的安全性问题，提出了如下的隔膜，所述隔膜具有通过在具有多孔的多孔聚合物基材的至少一个表面上涂布过量的无机粒子和粘合剂聚合物的混合物而形成的多孔有机-无机涂层。所述多孔有机-无机涂层中包含的无机粒子具有良好的耐热性，从而防止在电化学装置过热时，正极(或阴极)与负极(或阳极)之间的短路。
通常，通过经由浸涂法在多孔聚合物基材上形成有机-无机涂层的方法制造具有多孔有机-无机涂层的隔膜。然而，因为使用有机溶剂基浆料，所以该制造方法在制造电化学装置时具有安全隐患，且较不环保且较不具经济效益。
与有机溶剂基浆料相反，水性浆料安全、环保且经济效益高，但其高表面张力造成对聚烯烃基基材的低可湿性问题，限制了用于隔膜涂布的用途。
发明内容
技术问题
因此，本发明的一个目的为提供一种隔膜的制造方法，通过所述方法经由在多孔聚合物基材上涂布浆料的过程制成具有有机-无机复合多孔涂层的隔膜，在这种情况下，使用具有预定性质的水性浆料来改善对多孔聚合物基材的润湿性。
本发明的另一个目的为提供通过所述制备方法获得的隔膜。
本发明的再另一个目的为提供一种具有所述隔膜的电化学装置。
技术方案
为实现以上目的，本发明提供一种隔膜的制造方法，所述方法包括：准备包含无机粒子、粘合剂聚合物和水性介质的水性浆料，将所述水性浆料涂布在多孔聚合物基材的至少一个表面上，以形成有机-无机复合多孔涂层，
其中所述水性浆料的毛细管数为0.3至65，
毛细管数由以下等式1确定：
<等式1>
毛细管数(Ca)＝(μ×U)/σ
其中μ＝粘度(kgf·s/m2)，U＝涂布速度(m/s)，且σ＝表面张力(kgf/m)。
根据一个实施方案，提供一种通过所述制备方法获得的隔膜。
根据一个实施方案，提供一种电化学装置，其包含正极(或阴极)、负极(或阳极)和置于所述正极(或阴极)与所述负极(或阳极)之间的隔膜。
根据例示性的实施状况，所述电化学装置可以为锂二次电池。
有益效果
本发明通过提供一种隔膜的制造方法可以确保制造过程中的安全性和经济效率，所述方法使用水性浆料在多孔聚合物基材的表面上形成有机-无机复合涂层，且可以利用如上获得的隔膜来改善电化学装置的安全性。
具体实施方式
下文中，将对本发明进行详细说明。在说明前，应理解说明书及附属权利要求中所使用的术语不应被解释为限于一般及字典的含义，而应在允许发明人为了最好地解释而适当地定义术语的原则的基础上，基于对应于本发明的技术方面的意义和概念作出阐释。
根据一个实施方案的隔膜的制造方法包括：制备包含无机粒子、粘合剂聚合物和水性介质的水性浆料，和将所述水性浆料涂布在多孔聚合物基材的至少一个表面上，以形成有机-无机复合多孔涂层。
所述水性浆料的毛细管数可以由以下等式1确定：
<等式1>
毛细管数(Ca)＝(μ×U)/σ
其中μ表示粘度(kgf·s/m2)，U表示涂布速度(m/s)，且σ表示表面张力(kgf/m)。
毛细管数为用以确定水性浆料的可湿性的因素，通过适当地控制此因素，可以实现水性浆料对多孔聚合物基材的润湿，且可以有助于涂布。
毛细管数由水性浆料的粘度、涂布速度和表面张力确定，且粘度可以基于水性浆料的固体含量及供应温度而改变。涂布速度表示在将水性浆料涂布在基材上时的速度，且基于涂布速度，可以改变水性浆料对基材的润湿。当表面张力具有低的值时，实现润湿，使得更有利于施加浆料，且可以通过添加剂使此值最小化。
为了通过毛细管数确保水性浆料的最佳可湿性，由以上等式1确定的值可以具有在0.3与65之间的范围，例如，在0.5与45之间。在此范围内，可以在低表面张力下实现对多孔聚合物基材的润湿，可以有助于涂布。
可以将水性浆料的粘度调节至最佳范围，且在这种情况下，可以使用增稠剂。增稠剂不限于特定的类型，只要其为能够调节水性浆料的粘度的材料即可，但可以包括例如羧甲基纤维素、甲基纤维素、羟基甲基纤维素、乙基纤维素、聚乙烯醇、氧化淀粉、磷酰化淀粉(phosphorylated starch)、酪蛋白和它们的盐。单独地或以任何比率组合使用这些例示性增稠剂。当使用增稠剂时，相对于无机物，增稠剂对水性浆料的比率通常为0.1质量％以上，优选为0.5质量％以上，更优选为0.6质量％以上，且上限通常为5质量％以下，优选为3质量％以下，更优选为2质量％以下。当所述比率低于所述范围时，涂层经常显著减少。当所述比率高于所述范围时，有可能减少无机粒子或粘合剂在浆料中的含量。
水性浆料的粘度可以基于供给温度而改变，且粘度随着温度降低而增高且随着温度升高而降低。因此，通过选择最佳供给温度，可以适当地控制水性浆料的粘度。供给温度范围可以为例如10℃至50℃。
通过增稠剂调节的水性浆料的粘度可以具有在0.005kgf·s/m2与0.05kgf·s/m2之间的范围，例如，在0.01kgf·s/m2与0.25kgf·s/m2之间。
可以将水性浆料的涂布速度适当地调节至容易在多孔聚合物基材上涂布水性浆料的范围，即，确保可湿性的范围。涂布速度可以通过制造过程中例如诸如滚筒速度或张力的变量的机械控制而确定，且可以具有在10m/s与100m/s之间的范围，例如在30m/s与70m/s之间。当涂布速度超过该范围时，由于水性浆料涂布的劣化或制造过程时间延长而导致经济效率降低。
水性浆料的表面张力为确保在低表面能下对多孔聚合物基材的可湿性的重要因子，且优选赋予尽可能低的表面张力。为此，将添加剂引入到水性浆料中可以引发表面张力降低，所述添加剂可以包括乳化剂，确切地说，为亲水性表面活性剂，例如选自如下中的至少任一种亲水性表面活性剂：聚氧乙烯(10)-氢化蓖麻油、聚氧乙烯(40)-氢化蓖麻油、聚氧乙烯(60)-氢化蓖麻油、硅氧烷、聚山梨酯60、聚山梨酯80和聚山梨酯20。相对于水性浆料的重量，可以以约0.1重量％至约3.0重量％的含量添加所述添加剂。
通过添加剂可以将水性浆料的表面张力调节至在0.0015kgf/m与0.007kgf/m之间的范围内。
水性浆料中使用的水性介质可以为水或醇与水的混合物。所述醇可以包括但不限于甲醇、乙醇、丙醇、异丙醇、丁醇、叔丁醇和戊醇。
使用水性浆料涂布的多孔聚合物基材可以为多孔聚合物膜基材或多孔聚合物非织造基材。
作为多孔聚合物膜基材，众所周知，可以使用由诸如聚乙烯和聚丙烯的聚烯烃的多孔聚合物膜制成的隔膜，且聚烯烃多孔聚合物膜基材在例如80℃与130℃之间的温度下展现关闭功能。聚烯烃多孔聚合物膜可以由单独的或组合的聚烯烃基聚合物制成，所述聚烯烃基聚合物包括聚乙烯诸如高密度聚乙烯、线性低密度聚乙烯、低密度聚乙烯和超高分子量聚乙烯、聚丙烯、聚丁烯和聚戊烯。此外，可以使用包括聚酯以及聚烯烃的各种聚合物制造多孔聚合物膜基材。此外，多孔聚合物膜基材可以形成为至少两个膜层的堆叠结构，且各个膜层可以由聚合物例如如上所述的聚烯烃和聚酯单独或组合地形成。
可以由使用聚合物的纤维制造多孔聚合物非织造基材，所述聚合物包括如上所述的聚烯烃基聚合物或其它具有较高耐热性的聚合物，例如聚酯，诸如聚对聚对苯二甲酸乙二醇酯(PET)。类似地，可以由纤维单独或组合地制造多孔聚合物非织造基材。
基于期望的目的，可以不同地选择多孔聚合物膜基材的材料或形状。
对多孔聚合物基材的厚度无特别限制，但优选厚度在1μm至100μm的范围内，更优选为5μm至50μm，且对多孔聚合物基材的孔径和孔隙率无特别限制，但孔径和孔隙率分别优选为0.01μm至50μm和10％至95％。
将水性浆料涂布在多孔聚合物基材上的方法没有特别限制，但优选使用狭缝式涂布方法或浸涂法。狭缝式涂布是如下的一种涂布方法：将经由缝模供应的涂布溶液涂布在基材的前表面上，且可以基于自定量泵供应的流速来控制多孔涂层的厚度。浸涂为如下的一种涂布方法：将基材浸泡于含有涂布溶液的罐中，可以基于涂布溶液的浓度和从涂布溶液罐取出基材时的速度来控制多孔涂层的厚度，且为了进行更精确地厚度控制，可以进行在浸泡后通过迈耶棒(mayer bar)的后调节(post-metering)，之后，在烘箱中进行干燥，从而在多孔聚合物基材的两个表面上形成多孔涂层。
在其中将无机粒子分散于水性溶剂中且将粘合剂聚合物溶解或分散于所述水性溶剂中的浆料中，所述无机粒子没有特别限制，只要它们电化学稳定即可。即，本发明的可用的无机粒子不限于特别的类型，只要其在电化学装置应用的操作电压范围(例如，相对于Li/Li+为0至5V)中不造成氧化和/或还原反应即可。特别地，当将具有高介电常数的无机粒子用作无机粒子时，这种无机粒子可以有助于电解质盐(例如锂盐)在液体电解质中的离解度增高，且可以改善电解液的离子电导率。
由于上述原因，优选的无机粒子包括具有大于或等于5、优选大于或等于10的高介电常数的无机粒子。具有大于或等于5的介电常数的无机粒子包括作为非限制性实例的BaTiO3、Pb(Zr,Ti)O3(PZT)、Pb1-xLaxZr1-yTiyO3(PLZT，0<x<1，0<y<1)、Pb(Mg1/3Nb2/3)O3-PbTiO3(PMN-PT)、二氧化铪(HfO2)、SrTiO3、SnO2、CeO2、MgO、NiO、CaO、ZnO、ZrO2、Y2O3、Al2O3、勃姆石(boehmite)(γ-AlO(OH))、TiO2、SiC或它们的混合物。
此外，所述无机粒子可以包括能够传输锂离子的无机粒子，即含有锂原子且具有在不储存锂的情况下传输锂离子的功能的无机粒子。能够传输锂离子的无机粒子包括作为非限制性实例的磷酸锂(Li3PO4)、锂钛磷酸盐(LixTiy(PO4)3，0<x<2，0<y<3)、锂铝钛磷酸盐(LixAlyTiz(PO4)3，0<x<2，0<y<1，0<z<3)、(LiAlTiP)xOy基玻璃(0<x<4，0<y<13)诸如14Li2O-9Al2O3-38TiO2-39P2O5、锂镧钛酸盐(LixLayTiO3，0<x<2，0<y<3)、锂锗硫代磷酸盐(LixGeyPzSw，0<x<4，0<y<1，0<z<1，0<w<5)诸如Li3.25Ge0.25P0.75S4、锂氮化物(LixNy，0<x<4，0<y<2)诸如Li03N、SiS2基玻璃(LixSiySz，0<x<3，0<y<2，0<z<4)诸如Li3PO4-Li2S-SiS2、P2S5基玻璃(LixPySz，0<x<3，0<y<3，0<z<7)诸如LiI-Li2S-P2S5或它们的混合物。
此外，无机粒子的平均粒度没有特别限制，但为了形成具有均匀厚度和适当的孔隙率的多孔涂层，期望在0.001μm与10μm之间的范围内。当平均粒度小于0.001μm时，分散性可能会劣化，当平均粒度大于10μm时，多孔涂层的厚度可能会增加。
作为粘合剂聚合物，优选使用玻璃化温度(Tg)在-200℃与200℃之间的聚合物，其可以改善最后将形成的多孔涂层的机械性质，诸如可挠性和弹性。
此外，粘合剂聚合物并非必须具有离子传导能力，但当使用具有离子传导能力的聚合物时，可以进一步改善电化学装置的性能。因此，具有尽可能高的介电常数的粘合剂聚合物是优选的。实际上，因为盐在电解液中的离解度依赖于电解质溶剂的介电常数，所以随着粘合剂聚合物的介电常数增加，盐在电解质中的离解度可以得到改善。粘合剂聚合物的介电常数可以在1.0至100(在1kHz频率下测得)的范围内，尤其是优选大于或等于10。
粘合剂聚合物可以包括作为非限制性实例的丁苯橡胶(SBR)基聚合物和丙烯酸酯基聚合物。
无机粒子与粘合剂聚合物的重量比优选为例如在50:50与99:1之间的范围内，更优选在60:40与99:1之间，更加优选在70:30与95:5之间。当无机粒子对粘合剂聚合物的含量比低于50:50时，因为聚合物含量高，所以形成的多孔涂层的孔径和孔隙率可能降低。当无机粒子的含量高于99重量份时，因为粘合剂聚合物含量低，所以形成的多孔涂层的抗剥离性可能降低。
可以将乳液态的粘合剂聚合物分散于溶剂中，且为了有助于均匀混合和溶剂去除，可用溶剂的非限制性实例可以包括水、甲醇、乙醇、异丙醇或它们的混合物。
通过将粘合剂聚合物溶解在溶剂中并且添加并分散所述无机粒子可以制备其中将无机粒子分散在溶剂中且将粘合剂聚合物溶解在溶剂中的浆料。无机粒子可以在被粉碎至最佳尺寸后添加，但优选将无机粒子添加至粘合剂聚合物的溶液，之后在使用球磨方法粉碎无机粒子的同时分散无机粒子。
通过上述方法制造的有机-无机复合多孔涂层可以在对多孔聚合物基材的润湿性和因此的粘结性方面得到改善。在有机-无机复合多孔涂层中，当无机粒子堆积且彼此接触时，无机粒子通过粘合剂聚合物而彼此粘结，从而在无机粒子之间形成间隙体积，且无机粒子之间的间隙体积变成空隙而形成孔。
即，粘合剂聚合物使得无机粒子彼此粘附而保持粒子的粘合状态，例如，粘合剂聚合物连接且保持无机粒子。此外，有机-无机复合多孔涂层的孔是利用界定空隙的无机粒子之间的间隙体积形成的孔，且这是由无机粒子的密堆积或紧密堆积结构中基本上以表面接触的无机粒子所界定的空间。
可以通过在经以上方法制备的隔膜置于其间的条件下层压正极(或阴极)和负极(或阳极)构造电化学装置。所述电化学装置包括所有促进电化学反应的装置，例如，所有类型的一次和二次电池、燃料电池、太阳能电池和电容器诸如超级电容器。特别地，在二次电池中，期望有锂二次电池，所述锂二次电池包括锂金属二次电池、锂离子二次电池、锂聚合物二次电池或锂离子聚合物二次电池。
要与本发明的隔膜一起应用的电极没有特别限制，且可以以如下方式制造电极：通过本领域中已知的一般方法将电极活性材料粘合于电极集电器。在电极活性材料中，正极(或阴极)活性材料的非限制性实例包括通常可以用于电化学装置的正极(或阴极)的普通正极(或阴极)活性材料，特别优选为锂锰氧化物、锂钴氧化物、锂镍氧化物、锂铁氧化物或它们的复合氧化物。负极(或阳极)活性材料的非限制性实例包括通常可以用于电化学装置的负极(或阳极)的普通负极(或阳极)活性材料，特别优选为锂金属或锂合金，和锂吸附材料诸如碳、石油焦、活性炭、石墨及其它碳。正极(或阴极)集电器由作为非限制性实例的基于铝、镍或它们的组合物的箔制成，且负极(或阳极)集电器由作为非限制性实例的基于铜、金、镍、铜合金或它们的组合物的箔制成。
可以用于本发明的电化学装置的电解液可以为其中盐溶解或离解于有机溶剂中的电解液，所述盐具有由例如A+B-表示的结构：其中A+为碱金属阳离子，诸如Li+、Na+、K+、或它们的组合物且B-为阴离子，如PF6 -、BF4 -、Cl-、Br-、I-、ClO4 -、AsF6 -、CH3CO2 -、CF3SO3 -、N(CF3SO2)2 -、C(CF2SO2)3 -或它们的组合物，且有机溶剂包括但不限于碳酸亚丙酯(PC)、碳酸亚乙酯(EC)、碳酸二乙酯(DEC)、碳酸二甲酯(DMC)、碳酸二丙酯(DPC)、二甲基亚砜、乙腈、二甲氧基乙烷、二乙氧基乙烷、四氢呋喃、N-甲基-2-吡咯烷酮(NMP)、碳酸甲乙酯(EMC)、γ-丁内酯或它们的混合物。
基于制造方法和最终产品所需的物理性质，可以在电池制造过程的任何适当步骤中进行电解液的倾注。即，可以在电池组装前或在电池组装的最终步骤中实施电解液的倾注。
下文中，将通过实施例对本发明进行详细说明以帮助理解。然而，本发明的实施方式可以采用数种其它形式，且本发明的范围不应被解释为限于以下实施例。提供本发明的实施方式以向本发明所属的技术领域中的普通技术人员更充分地说明本发明。
实施例1
以90:6:4的比率将作为无机物的粒径为500nm的勃姆石(γ-AlO(OH))(NabaltecApyral AOH60)、作为粘合剂聚合物的丁苯橡胶(SBR)(JSR TRD102A)和作为增稠剂的羧甲基纤维素(CMC)(大赛璐化学工业株式会社(Daicel Chemical Industry 1220))进行混合，并在50℃的水中溶解约3小时或更久，之后使用球磨方法将无机粒子粉碎且分散于其中历经12小时或更久，以制备含有30％水平的固体的水性浆料。为降低所制备浆料的表面张力，添加对应于浆料重量的0.1％的乳化剂(道康宁67添加剂)。所制备浆料的粘度为0.007kgf·s/m2，且表面张力为0.0025kgf/m。
通过缝模(slot die)法在0.2m/秒的速度下将浆料涂布在12μm厚的多孔膜上(SKinnovation 512GK)，在使浆料通过温度调节至80℃的烘箱的同时干燥浆料中所包含的溶剂，制成具有调节至4μm的厚度的多孔涂层的隔膜。在以上条件下，毛细管数为0.56。生成的隔膜实现了均匀的厚度，宽度方向允许有1μm以下的偏差。
实施例2
通过进行与实施例1相同的方法来制造浆料和隔膜，不同之处在于将涂布速度变成1.5m/秒。在以上条件下，毛细管数为4.2，生成的隔膜实现了均匀的厚度，宽度方向允许有1μm以下的偏差。
实施例3
通过进行与实施例2相同的方法来制造浆料和隔膜，不同之处在于将浆料组成变成85:10:5。在以上条件下，毛细管数为24.0，生成的隔膜实现了均匀的厚度，宽度方向允许有1μm以下的偏差。
比较例1
通过进行与实施例1相同的方法来制造浆料和隔膜，不同之处在于没有使用乳化剂。在以上条件下，毛细管数为0.23。涂布过程中出现沟流现象，结果，无法在基材的整个宽度上形成均匀的多孔涂层。

Claims (19)

1.一种隔膜的制造方法，其包括：
准备包含无机粒子、粘合剂聚合物和水性介质的水性浆料；以及
将所述水性浆料涂布在多孔聚合物基材的至少一个表面上，以形成有机-无机复合多孔涂层，
其中所述水性浆料的毛细管数为0.3至65，
所述毛细管数由以下等式1确定：
毛细管数(Ca)＝(μ×U)/σ
其中μ表示粘度且单位为kgf·s/m2，U表示涂布速度且单位为m/s，且σ表示表面张力且单位为kgf/m，并且
所述粘度μ为0.005至0.05，且所述涂布速度U为0.15至2.0。
2.根据权利要求1所述的隔膜的制造方法，其中所述毛细管数Ca为0.4至45。
3.根据权利要求1所述的隔膜的制造方法，其中所述表面张力σ为0.0015至0.005。
4.根据权利要求1所述的隔膜的制造方法，其中所述水性介质为水，或醇与水的混合物。
5.根据权利要求1所述的隔膜的制造方法，其中所述多孔聚合物基材为多孔聚合物膜基材或多孔聚合物非织造基材。
6.根据权利要求5所述的隔膜的制造方法，其中所述多孔聚合物膜基材为聚烯烃基多孔聚合物膜基材。
7.根据权利要求6所述的隔膜的制造方法，其中所述聚烯烃基多孔聚合物膜基材由选自聚乙烯、聚丙烯、聚丁烯和聚戊烯中的至少一种聚合物形成。
8.根据权利要求1所述的隔膜的制造方法，其中所述多孔聚合物基材的厚度为5μm至50μm，且孔径和孔隙率分别为0.01μm至50μm和10％至95％。
9.根据权利要求1所述的隔膜的制造方法，其中通过狭缝式涂布方法进行所述有机-无机复合多孔涂层的形成。
10.根据权利要求1所述的隔膜的制造方法，其中通过浸涂法进行所述有机-无机复合多孔涂层的形成。
11.根据权利要求1所述的隔膜的制造方法，其中所述无机粒子的平均粒度为0.001μm至10μm。
12.根据权利要求1所述的隔膜的制造方法，其中所述无机粒子为选自如下的无机粒子：具有大于或等于5的高介电常数的无机粒子、能够传输锂离子的无机粒子和它们的混合物。
13.根据权利要求12所述的隔膜的制造方法，其中所述具有大于或等于5的高介电常数的无机粒子为选自如下中的任一种无机粒子或它们的混合物：BaTiO3；Pb(Zr,Ti)O3(PZT)；Pb1-xLaxZr1-yTiyO3(PLZT)，其中0<x<1且0<y<1；Pb(Mg1/3Nb2/3)O3-PbTiO3(PMN-PT)；二氧化铪(HfO2)；SrTiO3；SnO2；CeO2；MgO；NiO；CaO；ZnO；ZrO2；SiO2；Y2O3；Al2O3；勃姆石(γ-AlO(OH))；SiC和TiO2。
14.根据权利要求12所述的隔膜的制造方法，其中所述能够传输锂离子的无机粒子为选自如下中的任一种无机粒子或它们的混合物：磷酸锂Li3PO4；锂钛磷酸盐LixTiy(PO4)3，其中0<x<2且0<y<3；锂铝钛磷酸盐LixAlyTiz(PO4)3，其中0<x<2，0<y<1，且0<z<3；(LiAlTiP)xOy基玻璃，其中0<x<4且0<y<13；锂镧钛酸盐LixLayTiO3，其中0<x<2且0<y<3；锂锗硫代磷酸盐LixGeyPzSw，其中0<x<4，0<y<1，0<z<1，且0<w<5；锂氮化物LixNy，其中0<x<4且0<y<2；SiS2基玻璃LixSiySz，其中0<x<3，0<y<2，且0<z<4；和P2S5基玻璃LixPySz，其中0<x<3，0<y<3，且0<z<7。
15.根据权利要求1所述的隔膜的制造方法，其中所述无机粒子与所述粘合剂聚合物的重量比在50:50与99:1之间的范围内。
16.根据权利要求1所述的隔膜的制造方法，其中所述粘合剂聚合物为选自丁苯橡胶(SBR)基聚合物和丙烯酸酯基聚合物中的任一种或它们的混合物。
17.一种通过根据权利要求1至16中任一项所述的制造方法获得的隔膜。
18.一种电化学装置，其包含正极、负极和置于所述正极与所述负极之间的根据权利要求17所述的隔膜。
19.根据权利要求18所述的电化学装置，其中所述电化学装置为锂二次电池。
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CN105814711A (zh) 2016-07-27
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