CN1258830C - 含凝胶电解质的锂电池 - Google Patents
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Abstract
发现了一种锂电池,它包括一个负极、一个正极、一个隔膜。以及位于负极和正极之间的一种非水电解质溶液。至少负极材料和正极材料是被做成多孔型式,它能适应把负极、正极和隔膜粘合并贴压在一起的高分子材料。为降低电解质溶液升华的倾向,后者使电池周围包装材料膨胀,非水电解质溶液中包含能形成凝胶电解质的由锂盐、溶剂分子和一种聚合物的组成的溶液。
Description
本发明涉及一种锂电池,它至少包括:
一个含有负性电极材料和负性电流收集器的负电极;
一个含有正性电极材料和正性电流收集器的正电极;
一个把负极和正极分开的隔膜;
在负和正电极之间的一种非水溶电解质;其中至少负电极材料和正电极材料提供了多孔型式,后者可以适应把负电极、正电极和隔膜粘合并贴压在一起的高分子材料。
由于对轻型、便携式无线消费产品,诸如CD唱机、移动电话、膝上计算机(俗称笔记本电脑)和电视摄像机等日益增涨的市场需求,对高密度电池也有着增长的需要,具体地说,需要很薄和很柔韧性的电池。为提供可接受的轻便性,包含在所说的消费产品中的电池,应能以尽可能最小的重量和体积提供所必需的能量。然而,当电池做得愈薄时,为维持电池中各组份充分接触所需施加的压力也变得更为困难。
根据序言,从国际专利申请的公开号WO 00/04601中,已知一种电池。
所说的电池具有薄和柔韧的形式,并同时能提供很高的能量密度。还有,它以非常有效的方法维持了电极和隔膜之间的接触。这种电池可包装成薄壁的罐状,因为所说的罐壁不需要对电池的各个组份维持充分的压力。
在较高温度下,由低分子量有机分子制成的液体电解质,有时会趋向于升华,从而造成这种电池周围包装材料的膨胀。
本发明的一个目的是提供一种序言中那样的电池,其中上述问题得以避免。
这一目的是在序言中指定的电池中达到的,其特征为非水电解质包括由锂盐、溶剂分子和形成凝胶的聚合物(或聚合物胶凝剂)组成的溶液。
由于这类凝胶电解质具有较低的蒸气压,它在较高温度时呈现出比先有技术中所用的电解质大为降低的升华现象。这样,通过在正、负极之间提供凝胶电解质,即可防止在较高温度时电池组份周围包装材料的膨胀。
为了降低液体电解质升华的趋势,最好用聚合物胶凝剂。
这类聚合物胶凝剂可分别地引入到电池堆积物、阳极和阴极材料和/或隔膜中。在下面示例性的实施方案中,将描述各种类型的可以有益地使用的聚合物材料。
在一个优选的实施方案中,隔膜含有这种凝胶电解质,更优选地是隔膜是由这种凝胶电解质组成的。
在后一种实施方案中,这种凝胶电解质必须具有足够的机械强度,来用作正极和负极之间的隔膜。“通常的”隔膜从而被省去,而代之以这种凝胶电解质来作为隔膜。
在本发明的锂电池中,负电极(也称为阳极)基本上包含用于电池反应的负性电极活性材料和一个负性电流的收集器,后者用来在充电和放电时传输电子。
负性电极材料最好含有一种可嵌入的材料,优选碳,诸如无定形碳或石墨,它们可分散于一种聚合物粘合剂基质中。锂可被嵌入在碳的结晶层之间,例如以每1个锂原子对6个碳原子的量嵌入,换言之即LiC6。
正电极(也称为阴极)包括正性电极材料和一个正性电流收集器。
正性电极材料可包含嵌入锂的化合物,诸如LiMn2O4、LiCoO2或LiNiO2,它们可分散于聚合物粘合剂基质中。这种混合物也可包含粉状的导电材料,诸如碳黑(例如乙炔黑、热裂碳黑),石墨粉,金属粉末等。导电材料的量按重量计在2至15%范围内。
对于粘合剂基质聚合物,可使用的包括多糖、热塑性聚合物和具有像橡胶那样弹性的聚合物。其实例包括羧甲基纤维素、聚四氟乙烯、聚乙烯、聚丙烯和丁苯橡胶。这些聚合物可以单独使用或结合起来使用。聚合物粘合剂是用来把活性材料粉末粘合在一起,以防止它们裂解,并且固定这些粉末材料在电流收集器的表面上。聚合物粘合剂的用量按重量计在2至30%范围内。
对于电流收集器,可以使用任何电子导体,前提是它在电池中不会引发化学反应。正性电流收集器(阴极)材料的实例包括不锈钢、铝和镍。负性电流收集器(阳极)材料的实例包括不锈钢、铜和镍。收集器可以做成薄片、薄膜或薄板的形状。也可以是多孔的、穿孔的或筛状的。收集器的厚度一般在1至500微米范围内。
处于正和负电极之间的隔膜,可以是一种绝缘薄膜,它既有高的离子渗透性,也具有所需的机械强度。它可防止负极和正极之间发生短路,并可保持电解质溶液。一种通常使用的隔膜是由玻璃纤维制成的,或者是由烯烃聚合物诸如聚乙烯或聚丙烯做成的多孔薄片或无纺布。孔径一般在0.01至10微米范围内,隔膜厚度一般在5至300微米范围内。如上所述,通常的隔膜也可以用凝胶电解质本身来代替。
本发明的电池结构可以用任何数目的用作液体电解质的溶液来活化。作为溶剂,可使用酯类,诸如碳酸亚乙基酯、碳酸亚丙基酯、碳酸甲基乙基酯;醚类诸如四氢呋喃、二甲亚砜以及它们的混合物。溶质的实例包括由锂离子(Li+)和Lewis酸离子(BF4 -、PF6 -、AsF6 -、ClO4 -、CF3SO3 -)所形成的盐类以及它们的混合物。盐的浓度在0.5至2摩尔/升之间。
这种电池被封装在一个电池盒中,后者可以是塑料金属盒或塑料树脂盒。这些材料的实例包括不锈钢和像塑料似的聚丙烯。密封可通过粘合剂、焊接或焊剂来实施。扁平的柔韧性电池可被封装在不漏空气和湿气的盒袋中,后者可由涂布聚合物的铝箔制成。薄片诸如箔可在市场上买到,并可以它们的边上密封在一起。这种薄片通常包含外侧的15微米聚酯或聚乙烯膜、50微米的铝箔和内侧的15微米聚酯或聚乙烯膜并带有90微米的热密封粘合剂层。
本发明将更详尽地通过一种实施方案来阐明,其中描述了可有益地应用的各种类型的聚合物材料。
实施方案
通过把作为活性阳性材料的颗粒大小为10微米的6克石墨颗粒、4.5克羧甲基纤维素(1%水溶液)和0.5克作为粘合剂的丁苯橡胶(60%在水中的分散物)混合在一起,形成一种浆糊。涂布在铜箔电流收集器的两边表面上,从而制得负极材料的混合物。涂层厚度为200微米。铜箔的厚度为14微米。涂上所述糊的电流收集器在85℃预干燥15分钟,在110℃热处理3小时,然后压缩直到厚度为110微米。负电极被剪切成2×2厘米2的正方形。
通过把作为活性阳极材料的6克LiCoO2、0.18克作为导电材料的乙炔黑、5克羧甲基纤维素(1%的水溶液)和0.7克作为粘合剂的聚四氟乙烯(60%在水中的分散物)混合在一起,形成一种浆糊,涂布在铝箔电流收集器的两边表面上从而制得正极材料混合物。涂层的厚度为420微米。铝箔的厚度为20微米。糊好的电流收集器在85℃预干燥15分钟,在250℃热处理4小时,然后压缩直到厚度为100微米。正电极被剪切成2×2厘米2的正方形。
用25微米厚度的多孔聚乙烯薄片作为隔膜。
负极和正极各自通过机械穿孔来做成多孔型式,孔径一般约1毫米,这些孔分布成两维阵列,相互间的孔距为5毫米。
为制造本发明的锂电池,可形成负电极、隔膜和正电极的堆积。
然后把聚合物胶凝剂引入这种电池堆积中;引入阳极和阴极材料中和/或分别地引入隔膜中。随即通过往电池中引入电解质使电池活化。最好是使用以下类型的聚合物胶凝剂:
A)为产生化学交联的聚合物,可使用带有活泼基团的前体。这类分子的实例为具有以下一般结构的分子:
Y-B-X
其中X=Y=丙烯酸根、环氧基、乙烯基醚或硫杂环戊烯
X或Y=CH3
B=长链分子,诸如:
带有活泼基团的分子被溶解在一种溶剂中并引入电池组份中。活性端基可选择丙烯酸根、环氧基、乙烯基醚或硫代环戊烯。这些活性分子可以是单一官能团或多官能团的。单一官能团的分子永远应与多官能团的分子结合使用以获得交联。聚合反应可通过高能射线诸如电子和γ-射线来诱发,或在溶剂存在条件下或干燥后用热引发剂来引发。在所有情况下,在活化电池之前试样要干燥。在活化过程中当电解质被引入电池时交联的聚合物由于电解质而成为溶胀的。
B)为了产生物理交联的凝胶,使用半结晶的聚合物或一种共聚物是有益的。这种聚合物被溶解在一种溶剂中。电池组份被浸渍在溶液中。然后把溶剂从体系中提取或蒸发出来,只留下干燥的聚合物。在活化过程中当电解质引入电池中时会发生聚合物的部分地溶胀。这意味着聚合物链彼此保持着物理连接。连接点是微晶或共聚物的部分,它没有被电解质所溶解。各种聚合物的实例有以下这些:
X和Y的实例:
-O-CH2-CH2-CH2-
-O-CH2-CH2-CH2-CH2-
-O-CH2-CH2-
C)作为第三种优选的可能性,可用具有很高分子量的聚合物。这种聚合物如上述那样引入电池组份中。然而在目前情况下当电池被活化时这种聚合物会溶解于电解质中。不过无论如何由于这种聚合物很高的分子量,它会是高度缠结和高度粘稠的。能用于这一目的的聚合物的实例有聚甲基丙烯酸酯和聚苯乙烯,聚乙烯基甲基酮。
在A和B项下叙述过的聚合物也可被用来生产隔膜。这类隔膜也可以和不含胶凝剂的标准电极结合使用。
Claims (5)
1.一种锂电池,至少包含:
一个负电极,它包含负性电极材料和负电流收集器;
一个正电极,它包含正性电极材料和正电流收集器;
一个多孔隔膜,它把负电极和正电极分开;和
在负电极和正电极之间的一种非水电解质,其中至少负电极和正电极是被做成通孔型式,所述的通孔容纳将负极、正极和隔膜粘合和压制在一起的聚合物材料;其特征在于所述非水电解质是容纳在至少隔膜的孔隙中的凝胶电解质。
2.权利要求1的锂电池,其中正性电极材料和负性电极材料是多孔性的,且其中所述凝胶电解质容纳在正极、负极和隔膜的孔隙中。
3.权利要求1的锂电池,其特征在于凝胶电解质含有聚合物胶凝剂和锂盐溶液。
4.权利要求3的锂电池,其特征在于所述胶凝剂包含化学交联的或物理交联的或极高分子量的聚合物。
5.一种锂电池,至少包含:
一个负电极,它包含负性电极材料和负电流收集器;
一个正电极,它包含正性电极材料和正电流收集器;
一个隔膜,它把负电极和正电极分开;和
在负电极和正电极之间的一种非水电解质,
其中至少负电极和正电极是被做成通孔型式,所述的通孔容纳将负极、正极和隔膜粘合和压制在一起的聚合物材料;其特征在于所述非水电解质是凝胶电解质,该凝胶电解质形成所述隔膜。
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EP (1) | EP1183750A2 (zh) |
JP (1) | JP2003514352A (zh) |
CN (1) | CN1258830C (zh) |
WO (1) | WO2001035471A2 (zh) |
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- 2000-10-26 EP EP00993058A patent/EP1183750A2/en not_active Withdrawn
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JP2003514352A (ja) | 2003-04-15 |
EP1183750A2 (en) | 2002-03-06 |
CN1342335A (zh) | 2002-03-27 |
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