CN103563127B - 电池分离膜用微多孔性膜制造装置、使用其的制膜方法 - Google Patents

电池分离膜用微多孔性膜制造装置、使用其的制膜方法 Download PDF

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CN103563127B
CN103563127B CN201280025310.8A CN201280025310A CN103563127B CN 103563127 B CN103563127 B CN 103563127B CN 201280025310 A CN201280025310 A CN 201280025310A CN 103563127 B CN103563127 B CN 103563127B
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precursor film
film
micro
refrigerating gas
porous membrane
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CN103563127A (zh
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朴铉彩
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    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
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Abstract

本发明涉及用作充电电池分离膜的微多孔性膜制造装置及方法。本发明的微多孔性膜制造装置包括：T形模（20），通过喷嘴前端部对经熔融的部分结晶性树脂的熔融树脂进行压制以成型前驱膜；导辊（50），布置在所述T形模（20）的压制方向的下游侧，对前驱膜（F1）进行移动引导以拉伸至一定牵伸比；前驱膜冷却装置（40），通过在所述前驱膜的正面/背面或者两侧面分别提供沿着前驱膜的移动方向流动的冷却气体流以对前驱膜进行冷却；以及膜延伸装置，对经所述前驱膜冷却装置（40）冷却的膜施加单轴方向或双轴方向的拉伸力。

Description

电池分离膜用微多孔性膜制造装置、使用其的制膜方法
技术领域
本发明涉及用于制造微多孔性膜（microporousfilm）的装置及其方法。尤其是，本发明涉及微多孔性膜制造方法，该方法通过T形挤型模对部分结晶性树脂进行压制以成型前驱膜，并对该前驱膜进行热处理（annealing）并延伸以适合于电池的微多孔性分离膜。
背景技术
最近，随着诸如便携式通信设备、便携式笔记本电脑等的电子设备的普及和使用的剧增，要求作为电子设备电池的充电电池具有轻量化、高电流密度化以及自放电小的特性。
随着这种趋势，用于充电电池的分离膜（separator）被广泛采用形成有多个微孔的微多孔性膜，以确保电极间良好的离子渗透性。电池分离膜用微多孔性膜需要具有与电池特性相关的多种所需特性，其中尤其要求其具有高强度、高气孔率。分离膜的高强度化可减少随着薄膜化而发生的内部短路的缺陷，由此可以使得电池的超薄化变得可能。此外，分离膜的气孔率通过改善离子渗透性而对充放电特性起到影响。
制造这种微多孔性膜的方法包括干式法和湿式法。基于干式法的制膜方法中，如图1所示，通过“T”型模（T-die）2对从压制机1供给的熔融树脂进行压制以压制成型前驱膜F1，将该前驱膜F1接触到相对低温（80-120℃）的铸造辊（冷却辊）3并进行冷却固化以在前驱膜F1上形成层状结晶，并对由此获得的前驱膜F1进行包含低温延伸和高温延伸的一系列延伸工序以对前驱膜进行延伸，从而制造微多孔性膜。
通过所述现有的干式法制造的微多孔性膜中，在冷却由部分结晶性（semicrystalline）树脂熔融压制而成的前驱膜F1的过程中将形成层状（lamella）结晶，接着在低温延伸过程中随着相对脆弱的非晶部分（amorphousregion）破裂而形成气孔，其中非晶部分存在于形成在前驱膜F1的层状结构的结晶之间，并且在高温延伸工序中随着该气孔被扩张而在膜上形成微多孔性结构。
前驱膜的层状结晶结构的生成将受到熔融压制成型的前驱膜的冷却速度的直接且决定性的影响。根据通常已知的信息，前驱膜的冷却速度的加快将促进层状结晶形成，但是在前驱膜的冷却速度过快时则对作为层状生长阶段的二次结晶化造成不利影响。因此，需要适当地调节压制成型的前驱膜的冷却速度以使得微多孔性膜根据其用途具有适当的气孔度。
但是，根据所述现有的前驱膜制造方法，因为移动中的前驱膜是通过与旋转中的冷却辊接触而进行冷却，所以不仅会导致难以进行均匀冷却，而且还难以调节冷却速度。由此将导致难以调节微多孔性膜的气孔大小或气孔度，进而导致了在改善膜的气孔度和多孔性方面的技术局限性。
发明内容
本发明为了解决所述现有的微多孔性膜制造方法所具有的问题，其目的在于提供微多孔性膜制造方法及制造装置，通过使用冷却气体的冷却方式替代冷却辊接触方式，改善前驱膜的冷却方法，从而容易调节膜的气孔大小和气孔度。
此外，本发明的另一目的在于提供微多孔性膜制造装置，通过不使用诸如冷却辊或真空吸入装置的附带装置，使结构变得简单且设备成本变得相对较低。
为了实现所述目的，本发明的微多孔性膜制造方法包括：
通过T形模对经熔融的部分结晶性树脂的熔融树脂压制以成型前驱膜的步骤；以及
通过使相对低温的冷却气体与所述前驱膜进行接触以对前驱膜进行冷却的冷却步骤。
此外，本发明的微多孔性膜制造方法还包括：在比所述部分结晶性树脂的熔点低的温度下，沿着单轴方向或双轴方向对通过与所述冷却气体接触而经冷却的前驱膜进行延伸从而在膜上形成微气孔的延伸步骤。
所述延伸步骤包括：在比所述部分结晶性树脂的熔点低的温度下，对所述前驱膜进行热处理的步骤；在比所述部分结晶性树脂的熔点低的温度下，对经热处理的前驱膜进行延伸的低温延伸步骤；在相对比所述低温延伸步骤中的工序温度高且比所述膜的部分结晶性树脂的熔点低的温度下，对在所述低温延伸步骤中经延伸的膜进行延伸的高温延伸步骤；在比熔点低的温度下，对在高温延伸步骤中经延伸的膜进行热处理以进行热固定的步骤。
在所述延伸步骤中低温延伸步骤和高温延伸步骤包括：使用多个辊的单轴延伸和使用延伸机的双轴延伸。
所述前驱膜冷却步骤的特征在于，通过流入口使冷却气体流入，并且使得流入的冷却气体沿着所述前驱膜的压制方向在所述前驱膜的正面/背面中至少一侧进行流动并与所述前驱膜进行接触，从而对前驱膜进行冷却，其中流入口被布置成沿着压制方向与所述T形模的喷嘴前端部距离一定间隔。
所述冷却气体只要是以气体状态存在于常温中的气体即可，优选为空气、氮气、氦气中的任一种，并且被控制成维持在0至80℃的范围。冷却气体尤其优选为经过滤的空气，并且维持在20至40℃的范围。
在所述冷却步骤中冷却气体优选为以0.1至100/分钟的流量流过冷却气体通路。
用于所述压制成型的部分结晶性树脂为选自由聚烯烃、聚四氟乙烯、聚醛树脂、聚酯、聚酰胺、聚（4-甲基-1-丁烯）构成的群中的任一种树脂或者一种以上的混合物或者共聚物。
根据本发明的微多孔性膜制造装置包括：
T形模，通过喷嘴前端部对经熔融的部分结晶性树脂的熔融树脂进行压制以成型前驱膜；前驱膜冷却装置，通过提供沿着所述前驱膜的压制方向流动的冷却气体流，以通过该冷却气体对前驱膜进行冷却；导辊，布置在所述T形模的压制方向的下游侧，对经压制的前驱膜进行引导以拉伸至预定牵伸比；以及膜延伸装置，在比部分结晶性树脂的熔点低的温度下，对通过所述前驱膜冷却装置并由冷却气体进行冷却的膜进行延伸。
所述膜延伸装置包括：低温延伸装置，在比所述部分结晶性树脂的熔点低的温度下进行延伸；高温延伸装置，在相对比所述低温延伸步骤中的工序温度高且所述膜的部分结晶性树脂的熔点低的温度下，对在所述低温延伸中经延伸的膜进行延伸；以及热固定装置，在比熔点低的温度下，对在所述高温延伸步骤中经延伸的膜进行热处理以进行热固定。
所述延伸装置可以是多个延伸辊（未图示）或者是通常的双轴延伸机，其中多个延伸辊以可传送的方式支承膜并且根据各自的转速差对所支承的膜施加沿着单轴方向（膜的长度方向）的拉伸力以沿着单轴方向进行延伸，而通常的双轴延伸机沿着双轴方向（膜的长度方向或宽度方向）对膜进行延伸。
所述前驱膜冷却装置的特征在于，包括：冷却气体通路，向着正面或背面中至少一侧提供沿着所述前驱膜的压制方向流动的冷却气体流；以及流入口，布置成与T形模的喷嘴前端相隔一定距离以使得所述冷却气体流入至所述冷却气体通路的内部。
本发明的微多孔性膜制造装置的特征在于，还包括：空调机，用于从流入至所述冷却气体通路内部的冷却气体中过滤杂质并且对冷却气体的温度进行调节。所述冷却气体为空气，空调机将空气调节至20至40℃的范围。
如上所述的本发明，因为是通过冷却气体与前驱膜进行接触而对前驱膜进行冷却固化，所以无需使用诸如冷却辊或真空吸入装置的附带装置，从而使结构变得简单且设备成本变得相对较低。
此外，根据本发明，只需对冷却气体的温度和流量进行调节即可简单地对前驱膜的冷却速度进行调节，因此可以轻易调节膜的气孔度或气孔大小，由此可以稳定地制造具有均匀气孔度的高品质微多孔性膜。
附图说明
图1是现有的微多孔性膜制造装置的示意图。
图2是根据本发明的微多孔性膜制造装置的示意图。
具体实施方式
下面，将参照附图对本发明的优选实施例进行详细说明。
若参照图2先对根据本发明的微多孔性膜制造装置进行说明时，根据本发明的微多孔性膜制造装置包括：T形模20，通过喷嘴前端部21以恒定压力对在压制机10中经熔融的部分结晶性树脂进行压制以成型前驱膜F1；导辊50，布置在所述T形模的压制方向的下游侧并且对前驱膜进行引导以拉伸至预定牵伸比；前驱膜冷却装置40，在所述前驱膜F1的正面/背面中任一侧或者在两面上分别沿着前驱膜F1的移动方向提供冷却气体流以对前驱膜进行冷却；以及膜延伸装置，在比所述部分结晶性树脂的熔点低的温度下，对所述经冷却的膜进行延伸从而在膜上形成微气孔。
用于制造本发明的微多孔性的所述部分结晶性树脂可以是选自由聚烯烃、聚四氟乙烯、聚醛树脂、聚酯、聚酰胺、聚（4-甲基-1-丁烯）构成的群中的任一种树脂或者其一种以上的混合物或者其共聚物。
通过T形模20对所述部分结晶性熔融树脂进行压制以成型未形成气孔的前驱膜F1，并且使由此成型的前驱膜F1通过前驱膜冷却装置40并通过由前驱膜冷却装置40提供的冷却气体对前驱膜F1进行冷却，其中该前驱膜冷却装置40被布置在T形模的喷嘴前端部下方。
用于前驱膜冷却的冷却气体是选自空气、氮气、氦气中的任一种，并且维持在0至80℃的范围。在本发明中，用作冷却气体的气体不限于上述所列的气体，只要是以气体状态存在于常温中的气体，任意气体都可以被用作冷却气体。然而，冷却气体优选为空气，并且在送风机30中生成并在空调机31过滤杂质，而后温度调节至20至40℃的范围后被提供至所述膜冷却装置40。
贯穿本说明书全文，为了说明的便利，将图2的前驱膜F1的右侧面称为“正面”，而将前驱膜的左侧面称为“背面”。
在所述前驱膜冷却装置40中，分别在所述前驱膜F1的正面和背面布置块40a和块40b并使得相对的内侧面以一定间隔S相隔，从而在块40a与块40b之间形成冷却气体通路43，其中所述各个块40a、40b具有冷却气体引导通路41a、42b，该冷却气体引导通路41a、42b用于将从空调机31供给的冷却气体引导至所述冷却气体通路43，并且所述引导通路41a、42b的前端部具有流入口42a、42b，该流入口42a、42b使得引导通路的冷却气体朝着膜移动方向进行流入。
所述流入口42a、42b位于与T形模的喷嘴前端部21距离5至200mm的下方，优选为位于距离2至60mm的下方。因为所述流入口42a、42b的设置位置将决定前驱膜的冷却起始点，所以将对用于膜的气孔形成的结晶形成起到重要的作用。
当将冷却气体供给至所述前驱膜冷却装置40的冷却气体引导通路内时，则该冷却气体通过流入口42a、42b流入至冷却气体通路43从而沿着前驱膜的移动方向进行流动并与前驱膜接触以进行冷却。此时，冷却气体通过对前驱膜进行冷却，促进前驱膜上层状结构的结晶的形成。
此处，冷却气体在所述冷却气体通路43中优选为以0.1至100/分钟的流量进行流动。
布置于所述冷却装置40下方的导辊50通过支承前驱膜的下端以进行把持，从而使得通过膜冷却装置40的冷却气体通路43的前驱膜不会因冷却气体的流动而晃动。并且通过调节用于旋转驱动导辊50的旋转电机（未图示）的速度，调节导辊50的转速，由此将经压制的前驱膜F1以预定牵伸比进行引导。因此，所述导辊50优选为布置在前驱膜的压制方向（竖直方向）的下游侧。
本发明的制膜装置包括：延伸装置，在比部分结晶性树脂的熔点低的温度下，沿着单轴方向或双轴方向对经所述冷却装置40冷却的膜进行延伸从而在膜上形成微气孔。
所述延伸装置包括：低温延伸装置，在比所述部分结晶性树脂的熔点低的温度下进行延伸；高温延伸装置，在相对比所述低温延伸步骤中的工序温度高且比所述膜的部分结晶性树脂的熔点低的温度下，对在所述低温延伸中经延伸的膜进行延伸；以及热固定装置，在比熔点低的温度下，对在高温延伸步骤中经延伸的膜进行热处理以进行热固定。
所述延伸装置可以是多个延伸辊（未图示）或者是通常的双轴延伸机，其中多个延伸辊以可传送的方式支承膜并且根据各自的转速差对所支承的膜施加沿着单轴方向（膜的长度方向）的拉伸力以沿着单轴方向进行延伸，而通常的双轴延伸机沿着双轴方向（膜的长度方向或宽度方向）对膜进行延伸。
通过上述微多孔性膜制造装置制造微多孔性膜的过程如下。
1、前驱膜压制成型步骤
使由经熔融的部分结晶性树脂而成的熔融体通过T形模20，并被压制成型从而成型为前驱膜。
所述前驱膜F1以卷曲在导辊50的外周面上的状态得到支承，其中该导辊50被布置在压制方向（竖直方向）的下方并进行旋转。导辊50以恒定速度进行旋转并对膜进行引导以拉伸至一定的牵伸比。此时，通过改变导辊50的转速即可调节膜的压制牵伸比（Draftratio）。
2、前驱膜的冷却步骤
使所述前驱膜通过冷却装置40的冷却气体通路43，并通过与冷却气体接触而对膜进行冷却。
用于膜冷却步骤的冷却气体只要是以气体状态存在于常温中的气体即可，优选为空气、氮气、氦气中的任一种，并且被控制成维持在0至80℃的范围。冷却气体尤其优选为经过滤的空气，并且维持在20至40℃的范围。此外，在膜冷却过程中冷却气体优选为以0.1至100/分钟的流量流过冷却气体通路。
3、膜的延伸步骤
通过与所述冷却气体接触而经冷却的膜将经过一系列延伸工序而均匀地形成微细的气孔。
所述延伸步骤包括：在比所述部分结晶性树脂的熔点低的温度下，对经所述冷却过程冷却的膜进行热处理的步骤；在比所述部分结晶性树脂的熔点低的温度下，对经热处理的前驱膜进行延伸的低温延伸步骤；在相对比所述低温延伸步骤中的工序温度高且比所述膜的部分结晶性树脂的熔点低的温度下，对在所述低温延伸步骤中经延伸的膜进行延伸的高温延伸步骤；以及在比熔点低的温度下，对在高温延伸步骤中经延伸的膜进行热处理以进行热固定的步骤。
在所述低温延伸步骤中，根据施加到膜的长度方向或宽度方向的拉伸力，非结晶部分被破裂从而沿着延伸方向形成气孔，其中该非结晶部分位于形成在膜上的层状结晶之间。
在所述高温延伸步骤中，通过高温延伸，在所述低温延伸过程中形成于膜上的气孔被扩张从而形成为多孔性气孔。
以上对在T形模沿着竖直向下方向压制成型的微多孔性膜进行了说明，但是本发明也可以适用于沿着竖直向上方向压制成型膜的情况。
根据以上的根据本发明的微多孔性膜制造方法，只需对冷却气体的温度和流量进行调节即可对前驱膜的冷却速度进行调节，因此可以轻易调节膜的气孔度或气孔大小并且使气孔度变得均匀，由此可以稳定地制造高品质的微多孔性膜。

Claims (8)

1.一种微多孔性膜制造方法，其特征在于，包括：
通过T形模对部分结晶性树脂的熔融体进行压制成型以成型前驱膜的步骤；
通过使温度低于所述部分结晶性树脂的熔点的冷却气体与前驱膜进行接触以对前驱膜进行冷却的冷却步骤；以及
在比所述部分结晶性树脂的熔点低的温度下，沿着单轴方向或双轴方向对所述经冷却的膜进行延伸从而在膜上形成微气孔的延伸步骤，
其中，在所述前驱膜冷却步骤中，提供与所述前驱膜的两个表面倾斜地接触并且沿着所述前驱膜的压制方向流动的冷却气体流，以通过冷却气体与前驱膜的接触对所述前驱膜进行冷却。
2.如权利要求1所述的微多孔性膜制造方法，其特征在于，
所述冷却气体为选自空气、氮气、氦气中的任一种，并且被维持在0至80℃的范围。
3.如权利要求2所述的微多孔性膜制造方法，其特征在于，
所述冷却气体为空气，并且被维持在20至40℃的范围。
4.如权利要求1所述的微多孔性膜制造方法，其特征在于，
所述部分结晶性树脂为选自由聚烯烃、聚四氟乙烯、聚醛树脂、聚酯、聚酰胺、聚(4-甲基-1-丁烯)构成的群中的任一种树脂或者一种以上的混合物或者共聚物。
5.如权利要求1所述的微多孔性膜制造方法，其特征在于，所述延伸步骤包括：
在比所述部分结晶性树脂的熔点低的温度下，对所述前驱膜进行热处理的步骤；
在比所述部分结晶性树脂的熔点低的温度下，对经热处理的前驱膜进行延伸的低温延伸步骤；
在相对比所述低温延伸步骤中的工序温度高且比所述膜的部分结晶性树脂的熔点低的温度下，对在所述低温延伸步骤中经延伸的膜进行延伸的高温延伸步骤；以及
在比熔点低的温度下，对在高温延伸步骤中经延伸的膜进行热处理以进行热固定的步骤。
6.一种充电电池分离膜，所述充电电池分离膜由根据权利要求1至5中任一项所制造的微多孔性膜构成。
7.一种微多孔性膜制造装置，其特征在于，包括：
T形模，通过喷嘴前端部对经熔融的部分结晶性树脂的熔融树脂进行压制以成型前驱膜；
前驱膜冷却装置，通过提供沿着所述前驱膜的压制方向在所述前驱膜的正面和背面侧流动的冷却气体流，以通过所述冷却气体对前驱膜进行冷却；
一个以上的导辊，布置在所述T形模的压制方向的下游侧，对经压制的前驱膜进行引导以拉伸至预定牵伸比；以及
膜延伸装置，在比所述部分结晶性树脂的熔点低的温度下，沿着单轴方向或双轴方向对在所述冷却装置中经冷却而获得的膜进行延伸从而在膜上形成微气孔，
其中，所述前驱膜冷却装置包括：
冷却气体通路，用于提供沿着所述前驱膜的压制方向流动的所述冷却气体流；以及
流入口，以与T形模的喷嘴前端相隔一定距离的方式形成以使得所述冷却气体倾斜地流入至所述冷却气体通路的内部。
8.如权利要求7所述的微多孔性膜制造装置，其特征在于，
所述冷却气体为空气，并且所述冷却气体通路还包括：空调机，用于对流入至所述冷却气体通路内部的冷却气体的杂质进行过滤并且对冷却气体的温度进行调节。
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