CN103392257A - 锂离子电池 - Google Patents

锂离子电池 Download PDF

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CN103392257A
CN103392257A CN2012800092040A CN201280009204A CN103392257A CN 103392257 A CN103392257 A CN 103392257A CN 2012800092040 A CN2012800092040 A CN 2012800092040A CN 201280009204 A CN201280009204 A CN 201280009204A CN 103392257 A CN103392257 A CN 103392257A
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芦浦正
三代祐一朗
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Abstract

本发明是一种圆筒型锂离子二次电池。为了确保电池异常时产生的气体的排气通路,本发明的锂离子电池具有如下结构:在设极柱与电池罐内壁的距离为A、设该极柱与电极卷绕组间的距离为B的情况下,使B/A的值最优化,其中,上述极柱与在作为带状电极的长边方向的卷绕方向上断续地形成的长条状引线片焊接。

Description

锂离子电池
技术领域
本发明涉及锂离子电池的结构,特别涉及电池的极柱周边的结构。
背景技术
近年来,以环境问题为背景,不仅在混合动力电动车(HEV)、电动车(EV)、铲车、挖掘机等移动体中实现了以锂离子电池为代表的二次电池的应用,而且在UPS(不间断电源装置)、太阳光发电的电力储藏等产业用用途中也实现了以锂离子电池为代表的二次电池的应用。随着这种二次电池的用途扩大,需求大容量化、高能量密度化。另外,除了这些高性能化,安全性也成为重要的课题。作为二次电池,存在镍镉电池、镍氢电池、锂离子电池等。镍镉电池由于镉有毒等原因,正在进行向镍氢电池或锂离子电池的转换。在现有的二次电池之中,特别是锂离子二次电池适于进行高能量密度化,现在也积极地进行其开发。
这种镍氢电池、锂离子二次电池的主要结构包括:在表面形成有负极活性物质层的金属集电体(负极);保持电解质的分隔板;和在表面形成有正极活性物质层的其它的金属集电体(正极)。镍氢电池正极由镍氧化物构成,负极由贮氢合金构成。另外,锂离子二次电池正极由锂离子金属氧化物构成,负极由石墨等的碳材料构成。
作为电池结构,大致分为:将带状的负极、分隔板和正极卷绕成涡旋状而形成的卷绕型结构;和将长条状(长方形)的负极、分隔板和正极交替配置而形成的叠层型结构。在具有卷绕型结构的卷绕密闭式电池的情况下,必须要将电池罐中产生的气体迅速且顺畅地引导至排气阀附近,另一方面,如何配置将带状的负极·正极组与连接到电池端子的极柱电连接的引线片也成为决定气体的通道的主要因素
作为卷绕密闭式电池的气体排出机构,具有专利文献1所公开的发明。在专利文献1中公开:在多个引线片重叠地存在于极板卷绕组的端面和位于与其相对的位置的具有气体排气阀的电池盖之间的情况下,在卷绕极板时在极板上不将引线片的配置设为等间隔,而是预先错开相位,故意制造间隙来形成气体的通道,来应对气体的通路堵塞的不良。另外,有时也在设置于气体排气通路上的极柱设置孔,从而设置气体的通道。
现有技术文献
专利文献
专利文献1:日本特许第3633056号公报
发明内容
发明想要解决的问题
然而,也如专利文献1所记载的那样,由于极板的厚度不均匀,有时不能进行卷绕工序前的引线片的位置控制,难以确保气体的通路。本发明要解决的技术问题在于,在极板组的卷绕工序前不控制引线片的位置的情况下,改善电池内部产生的气体的排气效果。
用于解决问题的技术方案
作为本发明的卷绕密闭式电池的一个例子的锂离子电池具有开裂阀,该开裂阀在电池内部产生气体的情况下,当电池罐内因气体而超过规定压力时开裂,从而将气体排出到罐外。但是,若不考虑电池内部的气体的流路,则存在电池的内压达到电池罐强度的极限而导致电池膨胀、破裂的结果。
为了解决该问题,本发明采用如下结构:使电机卷绕组至极柱的距离B的大小相对于图2所示的卷绕密闭式电池的电池罐内壁至极柱的距离A最优化,由此在电池内部中产生的气体的流动、即对气体进行排气时,更加迅速且顺畅地控制气体的流动,将气体排出到罐外。
具体而言,认为通过采用以下的结构,能够解决技术问题。
一种锂离子电池,在电池罐中收纳有:在轴心卷绕正极电极、保持电解质的分隔板和负极电极而形成的电极卷绕组,其中,正极电极在表面形成有负极活性物质层,负极电极在表面形成有正极活性物质层;极柱,其配置于电极卷绕组与电池端子之间,用于电极卷绕组与电池端子的电连接;和引线片,以长条状形成在设置于正极电极和负极电极的一边的活性物质未涂敷部分,并且与极柱电连接,其中,当设电池罐内壁至极柱的距离为A、设电极卷绕组至极柱的距离为B时,B/A的值为1.4~2.6。
此时,优选B/A的值为1.6~2.0。
或者,也优选电极卷绕组与极柱之间具有间隙的结构。
或者,也优选在轴心与极柱的接合部配置有间隔物的结构。
或者,也优选极柱为圆柱状的结构。
发明效果
根据本发明,能够在基板组的卷绕工序前不控制引线片的位置的情况下,改善在电池内部产生的气体的排气效果,能够提供安全性更高的卷绕密闭式电池。
附图说明
图1是说明本发明的一个实施例的卷绕电极组的结构图。
图2是说明本发明的一个实施例的电池主要部分的截面图。
图3是说明本发明的一个实施例的电极部的放大图。
具体实施方式
为了确保电池的安全性,电池设有安全阀等安全机构部。能量密度高的大容量的锂离子二次电池,由于过充电等误使用、异物的混入等所致的短路等,与现有的锂离子二次电池相比,发生破裂、起火等情况下的受损规模较大。因此,能量密度高的大容量锂离子二次电池在热失控等异常时,需要将内部存在的能量排放到电池外部,以免发生破裂、起火。安全阀承担这样的功能,另外,使排气的通路最优化也很重要。
以下,参照附图对作为本发明中应用的实施方式的锂离子二次电池进行详细说明。图1表示本发明中能够应用的电极卷绕组展开图,图2表示本发明的锂离子电池的主要部分的截面图,图3表示本发明中能够应用的电极的放大图。
本实施方式是将电极卷绕组8收纳于圆筒状电池容器10的圆筒型电池。
如图1所示,电极卷绕组8是通过将带状的负极电极3和带状的正极电极1隔着分隔板2卷绕在轴芯4上而形成的。以下,对正极电极1和负极电极3的制造方法进行说明。
正极电极1的制作采用如下的方法。在作为活性物质的锰酸锂(LiMn2O4)粉末中,添加作为导电材料的磷片状石墨,添加作为粘结剂的聚偏氟乙烯。进一步,在其中添加作为分散溶剂的N-甲基吡咯烷酮,进行混炼,制作浆料。之后,将该浆料涂敷在铝箔的两个面,制作极板。此时,在极板的长度方向上的一个侧缘残留有宽约20mm的未涂敷部。然后,进行干燥、冲压、截断,获得正极板。在该未涂敷部设置图3所示的切口部。切除后剩余的部分为引线片9。通过上述的工序最终获得的就是正极电极1。
负极电极3的制作采用如下的方法,在作为活性物质的非晶碳原材料中,添加作为导电剂的乙炔黑,添加作为粘结剂的聚偏氟乙烯,在其中添加作为分散溶剂的N-甲基吡咯烷酮,进行混炼,制作浆料。之后,将该浆料涂敷在滚轧铜箔的两个面,制作极板。此时,极板的长度方向上的一个侧缘残留有未涂敷部。然后,进行干燥、冲压、截断,制得负极板。在该未涂敷部设置与正极电极1同样的切口,形成引线片9′。通过上述的工序最终获得的就是负极电极3。
作为电池的制造方法,采用如下所示的方法。将以上述的方法制成的正极电极1和负极电极3与聚乙烯制分隔板2一起卷绕。正极电极1的引线片9和负极电极3的引线片9′分别以位于电机卷绕组8的彼此相反侧的两端的方式卷绕。制成的电极卷绕组8为从其两端面大致在整个表面突出有引线片9、9′的状态。
然后,为了防止极柱5与电极卷绕组8的端面的接触,聚丙烯制的中空圆柱状的间隔物6配置于作为电极卷绕组8的中心轴的轴心4的大致延长线上。中空圆柱状的间隔物6与从圆柱形状的极柱5突出的突起部连接。另外,从正极电极1导出的引线片9以在圆柱形状的极柱5的外周部的整周与极柱接触的方式发生形变(图2)。通过使用圆柱形状的极柱5,能够在与引线片9接触时容易形变,能够防止引线片9的形变所致的截断。在接触后,将引线片9与极柱5的圆柱形状外周部进行超声波焊接,实现电导通,并且将剩余的部分切除。此处,通过各种改变间隔物6的高度,使距离B从2.9mm到8.7mm十阶段地改变,制造距离B不同的总计10种电池。另一方面,从负极电极3导出的引线片9′与负极的圆柱形状的极柱5′的连接操作也与上述的操作同样地进行。
然后,将电极卷绕组8插入圆筒状电池罐10,利用具有电解液注液口11、具有用于对在内部产生的气体进行排气的开裂阀7的电池盖12,将电池容器10的两侧开放部分密封。此时,在电池容器10的长度方向两端部的位置配置外部连接用的电池端子13。由此,极柱5、5′配置在电极卷绕组8与电池端子13之间,用于电极卷绕组8与电池端子13的电连接。之后,从位于电池盖12的电解液注液口11将规定量的电解液注入到电池容器内,并且将电解液注液口11密封,由此制造圆筒型锂离子电池。电解液使用在碳酸亚乙酯、碳酸二甲酯和碳酸二乙酯的混合溶剂中溶解有六氟磷酸锂(LiPF6)的溶液。
(实施例)
进行了通过上述的方法制造的锂离子电池的过充电试验。以下,利用图表,对本发明的实施例进行说明。图2是应用本发明的二次电池的主要部分的截面图。
在本发明中,设图中所示的圆筒状电池罐10的内壁至极柱5、5′的距离为A,设电极卷绕组8的边缘面至极柱5、5′的距离为B。表1表示对各个电池进行了试验的结果。表中的结果以○、△、×判定圆筒状电池罐10的概况,分别定义如下。○:与过充电试验前相同的概况,△:电池罐出现膨胀但没有问题,×:电池罐产生孔。另外,作为复合要素,也表示了引线片9、9′有无弯曲。对表中的结果,在本试验中○、△判定为安全,其中,评价为○的电池被判定为更加安全。
【表1】
Figure BDA00003676159100051
Figure BDA00003676159100061
○:与过充电试验前相同的情况,△:电池罐出现膨胀但没有问题,×:电池罐产生孔。
如表1所示,引线片9、9′的弯曲在B/A=1.0~1.4时存在,而在1.6~3.0时不存在,在存在的区域中,安全性在B/A=1.0~1.2时呈×,在B/A=1.4时呈△。
在B/A=1.0~1.4的区域,图2中的B的距离较短,引线片9、9′产生了弯曲。在引线片9、9′产生了弯曲的情况下,该部分的强度变弱,因此在过充电时容易裂开。另外,引线片9、9′如图3所示,在电极的一个边大致等间隔地配置,当卷绕该电极时,引线片9、9′在电极卷绕组8的中心部密集,因此过充电时的气体来不及排出,导致引线片9、9′裂开,导致短路的危险性增加。根据以上的结果可认为,B/A=1.0~1.2时的安全性的结果是×的结果。另外,可认为,对于B/A=1.4的电池,B的距离对从电极卷绕组8的中心部的气体排出有效,因此安全性的结果为△。可以认为这是因为距离B对气体排出奏效,对引线片9、9′裂开所致的短路部位的减少起作用。
另外,在不存在引线片9、9′的弯曲的B/A=1.6~3.0的区域,在B/A=1.6~2.0时进行了过充电试验。但是,B/A=2.2~3.0时安全性为×或△。该区域的安全性恶化的触发因素被认为是装入电池中的电解液量,而不是引线片9、9′的弯曲、从电极卷绕组8的中心部的气体排出。如上所述,距离B通过改变图2所述的间隔物6的厚度而进行调整,伴随于此,圆筒状电池罐10的长度变化。因此,电解液量也在设计上发生变化。锂离子电池在过充电时大量产生源自电解液的气体。产生的气体经过图2的A,到达开裂阀7,排出到外部。此时,产生的气体一边与圆筒状电池罐10的内部摩擦而产生摩擦热,一边被排出,因此,构成气体的流路的A部内壁的温度上升,容易产生形变。
实验的结果是,当B/A=2.2~2.6时,因为从装入电池中的电解液产生的气体而在A部附近产生电池罐的膨胀,所以安全性为△。但是,在B/A=2.8~3.0的区域中,在A部附近产生孔,安全性的结果为×。
根据以上的结果,能够在B/A=1.4~2.6mm的范围确认安全性。另外,尤其在B/A=1.6~2.0mm的范围能够确认更良好的安全性。
附图标记说明
1……正极电极,2……分隔板,3……负极电极,4……轴心,5、5’……极柱,6……间隔物,7……开裂阀,8……电极卷绕组,9、9′……引线片,10……圆筒状电池罐,11……电解液注液口,12……电池盖,13……电池端子。

Claims (5)

1.一种锂离子电池,其特征在于:
在电池罐中收纳有:
在轴心卷绕正极电极、保持电解质的分隔板和负极电极而形成的电极卷绕组,其中,所述正极电极在表面形成有负极活性物质层,所述负极电极在表面形成有正极活性物质层;
极柱,其配置于所述电极卷绕组与电池端子之间,用于所述电极卷绕组与所述电池端子的电连接;和
引线片,以长条状形成在设置于所述正极电极和所述负极电极的一边的活性物质未涂敷部分,并且与所述极柱电连接,其中,
当设所述电池罐内壁至所述极柱的距离为A、设所述电极卷绕组至所述极柱的距离为B时,B/A的值为1.4~2.6。
2.如权利要求1所述的锂离子电池,其特征在于:
所述B/A的值为1.6~2.0。
3.如权利要求1所述的锂离子电池,其特征在于:
所述电极卷绕组与所述极柱之间具有间隙。
4.如权利要求3所述的锂离子电池,其特征在于:
在所述轴心与所述极柱的接合部配置有间隔物。
5.如权利要求1所述的锂离子电池,其特征在于:
所述极柱为圆柱状。
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