CN1174502C - 电池隔膜 - Google Patents

电池隔膜 Download PDF

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CN1174502C
CN1174502C CNB998070300A CN99807030A CN1174502C CN 1174502 C CN1174502 C CN 1174502C CN B998070300 A CNB998070300 A CN B998070300A CN 99807030 A CN99807030 A CN 99807030A CN 1174502 C CN1174502 C CN 1174502C
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G·H·M·卡利斯
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    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
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    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
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    • B29C48/25—Component parts, details or accessories; Auxiliary operations
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/491—Porosity
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    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
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Abstract

本发明涉及一种至少包括聚乙烯的微孔薄膜，上述聚乙烯具有大于5dl/g的特性粘度和最高为70vol.%的孔隙率，其特征在于薄膜具有至少为2.5的电池隔膜品质因数(F)，F＝BW.PR/(G.t)，其中BW为基本重量(g/m2)，PR为抗穿刺性(g)，G为Gurley值(sec/50ml)，t为薄膜厚度(μm)。本发明还涉及制备这种薄膜的方法，薄膜作为电池隔膜的用途，用本发明的薄膜生产的电池。

Description

电池隔膜
本发明涉及一种至少包括聚乙烯的微孔薄膜，上述聚乙烯具有大于5dl/g的特性粘度(在十氢化萘(decaline)中135℃下测量)以及最高为70vol.％的孔隙率。本发明尤其涉及适用作电池隔膜的微孔薄膜。
这种微孔薄膜可以从JP-A-08034873获知。在JP-A-08034873的实施例27中描述了含有聚乙烯的微孔膜，该聚乙烯具有14dl/g的特性粘度和52.5vol.％的孔隙率。适合用作电池隔膜的薄膜最好尽可能的薄。由于此原因，孔隙率最高为70vol.％。每单位面积和每单位厚度的薄膜重量最好尽可能的大，薄膜最好具有最高可能的耐刺破性能，以防止在薄膜的缠绕过程中受到电极尖端的损伤。适合用作电池隔膜的薄膜还具有最高可能的导电性。由于导电性取决于开孔数，用Gurley值表达的空气渗透性是衡量导电性的标准。根据ASTM标准D726，Gurley值确定为s/50ml，上述标准采用的测量面积为6.45cm2(1平方英寸)，重量567克。低Gurley值意味着薄膜具有高空气渗透性，因此也具有高的导电性。
本发明的目的是提供一种微孔薄膜，结合了上述的所有性能，比已知的薄膜更适合用作电池隔膜。
此目的的实现是因为薄膜具有至少为2.5的电池隔膜品质因数(F)
                F＝BW.PR/(G.t)
其中BW为基本重量(g/m2)，PR为抗穿刺性(g)，G为Gurley值(s/50ml)，t为薄膜厚度(μm)。
这些使薄膜具备用作电池隔膜所希望的优于现有薄膜的更加理想的性能组合。
在本文中的“特性粘度”应理解为根据ASTM D 4020，在十氢化萘(decaline)中135℃下测量的特性粘度(dl/g)。
“抗刺破性”在本文中应理解为根据DIN53373(g)测量的抗刺破性。
“Gurley”在本文中应理解为根据ASTM D 726(sec/50ml)测量的Gurley值。薄膜厚度(t)是根据ISO4593(μm)测量的厚度。
本发明还涉及根据本发明制备微孔薄膜的方法。已知的制备微孔薄膜的方法在JP-B-8-34873中描述。它描述通过下述步骤制备微孔聚乙烯膜的方法：将特性粘度大于5dl/g的均匀的聚乙烯溶液形成薄膜，冷却薄膜，双轴向地拉伸已冷却的薄膜。
此方法的缺点在于在JP-A-08034873中描述的方法不能用于生产电池隔膜品质因数为2.5或更高的微孔薄膜。
本发明的目的是提供一种方法，可以生产出电池隔膜的品质因数至少为2.5的微孔薄膜。
此目的是这样实现的：在低于溶剂中聚乙烯溶解温度的温度下，在拉伸之前通过蒸发的方式从薄膜中去除易蒸发的溶剂，使拉伸后的薄膜通过砑光机。
已知的聚乙烯溶剂被用作易蒸发的溶剂，例如脂肪族的、脂环族的、芳香族的烃，例如甲苯，二甲苯，四氢化萘，十氢化萘(decaline)，C6-C12烷烃或石油馏分，也可以是卤代烃，例如三氯苯和其它已知溶剂。考虑到溶剂的去除，优选采用在大气压力下沸点低于210℃的溶剂，几乎上述所有溶剂都满足此条件。
为了由聚乙烯溶液生产薄膜，所采用的必须是特性粘度大于5dl/g的均匀的聚乙烯溶液。均匀的聚乙烯溶液的连续制备可以采用已知技术来实现，例如在挤压机中。此技术的使用所表现的优点在于溶液可以用单一的连续操作制备并且挤压成薄膜，或者用其它方法加工成薄膜。本发明并不限于此技术，用不同方法制备的均匀溶液也可加工出微孔薄膜对本领域普通技术人员来说是显而易见的。
溶液中聚乙烯的浓度可以是宽范围内的不同取值，通常根据实际情况在2-50wt.％之间选择。溶液中含有的聚乙烯少于大约2wt.％时，生产出易碎的薄膜，进一步的加工变得非常困难。另一方面，当浓度高于30wt.％时，尤其高于50wt.％时，加工溶液变得相当困难。所含聚乙烯的浓度为50wt.％或以上的浓缩溶液虽然是可能采用的，然而不是很可取的，因此也在本发明的范围之内。在具有相同的总体浓度时，部分聚乙烯在溶解之前交联时，溶液的加工性能在某些情况下证明要好于溶液中仅含有非交联的聚乙烯的溶液。
薄膜由聚乙烯溶液形成。这可以采取不同的方法，例如借助于带有非常宽的狭缝形喷嘴的喷丝头进行纺丝，采用挤压或浇铸到轧辊或带子上的方式。
在聚乙烯溶液被加工成薄膜之后，由溶液构成的薄膜被冷却。这可通过使薄膜经过含有冷却剂的冷却浴实现。最好采用的是聚乙烯在其中不溶解的冷却剂。非常适用的冷却剂是水。然后降低温度从而在薄膜上形成胶凝，为进一步加工提供了足够结实和稳定的结构。冷却到周围温度甚至更低的温度是有可能的，但是由于在下一步的加工过程中溶剂必须从薄膜中蒸发，很清楚为了获得有益的加工，非常希望通常保持温度尽可能的高。这将限制热量的供应，需要通过蒸发从薄膜中尽可能多的去除溶剂。
接着，在低于溶解温度的温度下，溶剂从薄膜中蒸发。溶解温度是指高于所涉及的聚乙烯在溶剂中均匀溶解的温度。当溶液冷却到低于溶解温度，会产生胶凝。在溶解温度和胶凝温度之间有一限定性范围。在那种情况下溶剂是在根据本发明的加工过程中，在低于那些温度中的较低值的温度下从薄膜上蒸发。
如果所用的成形技术允许，薄膜可以选择性地预拉伸，这意味着导出或从浴内运送已胶凝的薄膜的线性速率不同于薄膜由溶液形成的线性速率。例如所选用的是挤压加工，后者速率是溶液从缝口挤压模头流出的线性速率。在该上下文中预拉伸被定义为如上所述的运输或导出速率和上述流出速率的商。
在薄膜形成以后，溶剂的蒸发的过程中，薄膜有收缩的趋势。为了获得微孔薄膜，可以通过至少在一个方向上使薄膜在平面状态下展开而阻止此收缩量。为此薄膜可以用简单的方式夹住。如果薄膜在两个方向上夹住，厚度方向是唯一会减薄的方向而且厚度实际上的确减薄了。某些相似情况也适用，例如管型膜和中空细丝。不但收缩可以被阻止，而且甚至可能在溶剂蒸发的过程中实现一个或两个方向上的拉伸。
溶剂从薄膜中蒸发了之后，薄膜在一个或多个方向上受到拉伸。对溶剂已经被清除的薄膜进行的拉伸可以选择性地在高于通过蒸发去除溶剂过程中拉伸所发生的温度下发生，但所提供的此更高的温度不能达到高于聚乙烯溶解的温度以至于导致溶解断裂。
砑光机的压力可以在10-150kg/cm之间。当压力低于10kg/cm，电池隔膜品质因数有时会小于2.5。当压力高于150N/mm，Gurley值会有不希望的增加。
优选的砑光机的压力范围为25-50kg/cm。在此范围内可以确保电池隔膜的品质因数大于3。
在经过输出辊的薄膜上施加2-3N/cm2张力也是有可能的。
本发明还涉及本发明薄膜作为电池隔膜的用途。
本发明还涉及包含本发明薄膜的电池。

Claims (6)

1.一种至少包括聚乙烯的微孔薄膜，上述聚乙烯具有大于5dl/g的特性粘度和最高为70vol.％的孔隙率，其中薄膜具有至少为2.5的电池隔膜品质因数F：
                F＝BW.PR/(G.t)，
其中BW为基本重量，以g/m2计；PR为抗穿刺性，以g计；G为Gurley值，以sec/50ml计；和t为薄膜厚度，以μm计。
2.根据权利要求1所述的微孔薄膜，其特征在于F大于3。
3.权利要求1所述的特性粘度大于5dl/g的聚乙烯微孔薄膜的制备方法，所述特性粘度是在十氢化萘中135℃下测得的，所述制备方法是通过以下步骤：
将均匀的聚乙烯溶液形成薄膜，
冷却薄膜，以使薄膜上出现胶凝，其特征在于：
在低于溶解温度的温度下，从薄膜上蒸发溶剂，溶剂为易蒸发的溶剂；
对薄膜在一个或多个方向上进行拉伸操作；和
通过砑光机。
4.根据权利要求3所述的方法，其中砑光机的压力为25-50kg/cm。
5.根据权利要求1或2的薄膜的用途，用作电池隔膜。
6.含有权利要求1或2所述薄膜的电池。
CNB998070300A 1998-06-05 1999-06-03 电池隔膜 Expired - Lifetime CN1174502C (zh)

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IL140061A (en) 2004-09-27
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US20010038947A1 (en) 2001-11-08
US6558591B2 (en) 2003-05-06
EP1092243A1 (en) 2001-04-18
DK1092243T3 (da) 2003-06-30
JP4256591B2 (ja) 2009-04-22
DE69905719T2 (de) 2004-02-05
IL140061A0 (en) 2002-02-10
JP2002518524A (ja) 2002-06-25
CN1304556A (zh) 2001-07-18
WO1999065093A1 (en) 1999-12-16
KR20010052564A (ko) 2001-06-25
AU4174099A (en) 1999-12-30
KR100621302B1 (ko) 2006-09-13

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