CN116259854A - 锂离子二次电池的制造方法 - Google Patents
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Abstract
一种锂离子二次电池的制造方法,包含:制作包含正极层、隔膜和负极层的电极体;将所述电极体和电解液封入外装体从而组装电池单元;以及使袋状构件和所述电池单元交替层叠,在沿着所述电池单元的层叠方向对所述电池单元进行恒压约束的状态下进行初始充电直至达到初始充电电压,所述袋状构件在其内部密封有流体。上述锂离子二次电池的制造方法能够均匀地对电极施加约束压。
Description
技术领域
本公开涉及一种锂离子二次电池的制造方法。
背景技术
锂离子二次电池被广泛用作个人计算机和便携终端等的便携式电源、电动汽车和混合动力汽车等的车辆用电源。特别是锂离子二次电池作为车辆用电源要求进一步的高容量化。
然而,锂离子二次电池在初始充电时,电解液和添加剂成分的一部分或电池构件所含的水分在电极表面发生分解,由此产生气体。该气体的产生成为电池特性不良的主要原因。因此,作为该气体的除去方法,例如日本特开2013-125650公开了在初始充电时通过对锂离子二次电池施加约束压来脱气。此外,日本特开2013-125650公开了在初始充电结束后通过放置来进一步脱气的方法。
另外,如果在初始充电时对电池施加约束压,则电极中的活性物质层等可能破损。因此,为了抑制这样的破损,日本特开2020-107389公开了在初始充电时用弹簧式约束机构对电池进行恒压约束,在初始充电结束后用约束夹具对电池进行定尺寸约束的方法。
发明内容
但是,日本特开2013-125650的方法中,在对锂离子二次电池均匀地施加约束压方面仍存在改善的余地。特别是在制造高容量且电极面积大的锂离子二次电池时,初始充电时的气体产生量很大。因此,难以对锂离子二次电池均匀地施加约束压。
另外,日本特开2020-107389的方法中也同样存在改善的余地。特别是在电极面积大的电池的情况下,在电极的中央部和电极的端部施加的约束压产生不均。因此,由于电极层或固体电解质层开裂以及锂离子传导路径或电子传导路径中断,可能对电池特性造成影响。
因此,本公开的目的是提供一种锂离子二次电池的制造方法,其能够均匀地对电极施加约束压。
[1]本公开的锂离子二次电池的制造方法,包含以下工序:
制作包含正极层、隔膜和负极层的电极体;
将所述电极体和电解液封入外装体从而组装电池单元;以及
使袋状构件和所述电池单元交替层叠,在沿着所述电池单元的层叠方向对所述电池单元进行恒压约束的状态下进行初始充电直至达到初始充电电压,
所述袋状构件在其内部密封有流体。
根据上述[1]的制造方法,能够对电极均匀地施加约束压。
即,袋状构件和电池单元交替层叠。在袋状构件的内部封入有流体。流体能够产生各向同性的压力。因此,通过由袋状构件夹住电池单元,能够对电池单元的电极均匀地施加约束压。
[2]在上述[1]记载的锂离子二次电池的制造方法中,也可以还具备控制所述袋状构件的压力的压力控制机构。
[3]在上述[1]或[2]记载的锂离子二次电池的制造方法中,也可以还具备调节所述电池单元的温度的温度调节机构。
[4]在上述[1]~[3]中任一项记载的锂离子二次电池的制造方法中,也可以还具备流体放出机构,在所述电池单元的温度超过阈值温度的情况下,通过所述流体放出机构放出所述袋状构件的内部的流体。
附图说明
以下,参照附图说明本公开的示例性实施例的特征、优点以及技术和工业意义,其中相同的符号表示相同的元件。
图1是表示实施方式的锂离子二次电池的电极体一例的概略图。
图2是表示在实施方式中约束电池单元的方法的示意图。
具体实施方式
以下,说明本公开的一实施方式。不过,本公开并不限定于此。在本公开中,锂离子二次电池可以是液体系电池,也可以是全固体电池。再者,有时将锂离子二次电池简称为"电池"。
[实施方式1]
<锂离子二次电池的制造方法>
本实施方式中的锂离子二次电池的制造方法包含"(A)电极体的制作"、"(B)电池单元的组装"、"(C)电池单元的约束和初始充电"。
《(A)电极体的制作》
本实施方式的锂离子二次电池的制造方法包括形成电极体40的工序,电极体40包含正极层10、隔膜30和负极层20。
图1是表示本实施方式的锂离子二次电池的构成要件一例的概略图。电极体40包含正极层10、隔膜30和负极层20。隔膜30将正极层10与负极层20分离。正极层10与正极端子(未图示)连接。负极层20与负极端子(未图示)连接。
电极体40是层叠型的。电极体40也可以是卷绕型的。通过层叠正极层10、隔膜30和负极层20而形成电极体40。电极体40只要分别包含1层以上的正极层10、隔膜30和负极层20,就可以具有任意的层叠结构。例如,可以通过依次层叠正极层10、隔膜30、负极层20、隔膜30和正极层10而形成电极体40。
正极层10与隔膜30紧密接触。正极层10包含正极集电箔11和正极合剂层12。正极集电箔11例如可以是铝(Al)箔等。
正极合剂层12至少含有正极活性物质。正极合剂层12例如可以实质上由正极活性物质构成。正极合剂层12除了正极活性物质以外,例如还可以含有导电材料和粘合剂等。正极活性物质例如可以含有选自钴酸锂、镍酸锂、锰酸锂、镍钴锰酸锂等(例如Li1.15Ni1/3Co1/ 3Mn1/3O2等)、镍钴铝酸锂和磷酸铁锂中的至少一种。也可以对正极活性物质实施表面处理。通过表面处理,可以在正极活性物质表面形成缓冲层。缓冲层例如可以含有铌酸锂(LiNbO3)等。导电材料例如可以含有导电性碳材料等(例如气相成长碳纤维(VGCF)等)。粘合剂例如可以含有聚偏二氟乙烯(PVdF)等。
隔膜30介于正极层10与负极层20之间。隔膜30将正极层10和负极层20在空间上分开。隔膜30阻断正极层10与负极层20之间的电子传导。在本实施方式的电池是液体系电池的情况下,隔膜30是多孔质的。在隔膜30的多孔质部分浸渍有具有锂离子传导性的电解液。在本实施方式的电池是全固体电池的情况下,具有锂离子传导性的固体电解质层发挥隔膜30的作用。隔膜30例如也可以是聚烯烃制的。隔膜30例如可以具有单层结构。隔膜30例如可以由聚乙烯(PE)层构成。隔膜30例如可以具有多层结构。隔膜30例如可以具有三层结构。隔膜30例如可以包含聚丙烯(PP)层、PE层和PP层。PP层、PE层和PP层可以按此顺序层叠。
负极层20与隔膜30紧密接触。负极层20包含负极集电箔21和负极合剂层22。负极集电箔21例如可以是铜(Cu)箔、镍(Ni)箔等。
负极合剂层22至少含有负极活性物质。负极合剂层22例如可以实质上由负极活性物质构成。负极合剂层22除了负极活性物质以外,例如还可以含有导电材料和粘合剂等。负极活性物质例如可以含有选自石墨、软碳、硬碳、硅、氧化硅、硅基合金、锡、氧化锡、锡基合金和钛酸锂(Li4Ti5O12)中的至少一种。
《(B)电池单元的组装》
本实施方式的锂离子二次电池的制造方法包含:将电极体和电解液封入外装体从而组装电池单元。
外装体可以具有任意形态。外装体例如也可以是金属制的容器等。外装体例如也可以是铝层压膜制的小袋等。外装体例如可以是方形的,也可以是圆筒形的。外装体例如也可以具有用于注入电解液的注入口。
电解液包含支持电解质和有机溶剂。向外装体注入电解液。在电极体中浸渗电解液。注入电解液后,使外装体密闭。通过以上步骤,组装电池单元。
《(C)电池单元的约束和初始充电》
本实施方式的锂离子二次电池的制造方法包含:使袋状构件和电池单元交替层叠,在沿着电池单元的层叠方向对电池单元进行恒压约束的状态下进行初始充电直至达到初始充电电压。袋状构件在其内部密封有流体。
图2是表示在本实施方式中对电池单元进行恒压约束的方法的示意图。以下,示出采用该方法对电池单元100进行恒压约束的方法,但以下所示的对该电池单元100进行恒压约束的方法不过是例示。
如图2所示,该方法中,多个电池单元100和多个袋状构件51交替层叠,在沿电池单元100层叠方向夹持而相对的一对端板50a与50b之间,配置多个电池单元100和多个袋状构件51。即,各电池单元100被夹在一对端板50a与50b之间。而且,各电池单元100以隔着袋状构件51相邻的方式配置。各电池单元100被配置成在正极层10、隔膜30和负极层20的层叠方向上施加约束压。再者,如果端板50与电池单元100直接接触,则外装体可能破损或损伤。因此,优选在端板50与电池单元100之间配置袋状构件51。
在如上所述地配置后,通过封入袋状构件51内部的流体的压力,对电池单元100施加约束压。由此,电池单元100被约束。
对电池单元施加的压力没有特别限制。再者,在施加的压力小的情况下,可能无法对电池单元100均匀地施加约束压。另外,在施加的压力大的情况下,电池单元可能变形,袋状构件可能破损。因此,施加的压力例如在10kPa以上且50kPa以下的范围适当调整即可。
在此,对本实施方式的恒压约束与以往的恒压约束的差异进行说明。如日本特开2020-107389也公开的那样,以往,一般使用弹簧式约束机构进行恒压约束。但是,在弹簧式约束机构中,初始充电时电池单元膨胀和收缩时,弹簧会发生不少位移。即,由于电池单元本身的膨胀和收缩,使弹簧伸缩。因此,在一定压力范围内能够实现恒压约束。但是,未必能保持一定的压力。另外,随着电池单元的膨胀和收缩,进行充放电的端子不可避免地在约束轴向上移动,需要在充放电设备中设置追随端子移动的机构。
另一方面,本实施方式的恒压约束,使用在其内部封入了流体的袋状构件。由于流体能够产生各向同性的压力,因此能够对电池单元均匀地施加压力。另外,袋状构件中,即使初始充电时电池单元膨胀和收缩,袋状构件也会吸收电池单元厚度的变化量。因此,能够实现恒压约束。而且,由于也没有如上的充放电时的端子移动,所以不需要在充放电设备中设置追随端子移动的机构。
(袋状构件)
袋状构件由即使约束电池单元也不破损,能够对电池单元施加一定压力的材料构成。袋状构件的具体材料适当选择即可。在约束压低的情况下,作为材料,例如可举出用纸类将聚丙烯等塑料片复合化而成形为袋状的材料等。在约束压为中等程度的情况下,作为材料,例如可举出在汽车的气囊所代表的尼龙织物或聚酯织物上被覆了有机硅树脂的材料等。在约束压高的情况下,作为材料,例如可举出用芳族聚酰胺等高强度纤维增强的氯丁橡胶等。
流体可以是气体也可以是液体。作为气体,例如可举出空气等,作为液体,例如可举出水等。
(端板)
一对端板在电池单元的层叠方向上夹持袋状构件和电池单元而相对。端板的形状可以是任意形状。
端板的材料可以使用强度在恒压约束时不破损的程度的任意材料。例如,可举出铁、SUS(不锈钢)、铝合金等金属、碳纤维强化塑料、玻璃纤维强化塑料等纤维强化塑料等。
(初始充电)
初始充电在常温(25℃±5℃左右)下进行即可。根据使用的电解液等,初始充电电压不同,但初始充电电压例如可以为1V以上且5V以下、1.5V以上且4.5V以下或2V以上且4V以下。
另外,初始充电电压的调整可以通过恒电量充电(CC充电)来进行,例如可以是0.1C以上且10C以下左右、0.1C以上且5C以下左右或0.1C以上且2C以下左右。或者,初始充电也可以通过从充电开始直至达到规定电压为止以恒流进行,进而以恒压充电规定时间的恒流-恒压充电(CC-CV充电)来进行。
(压力控制机构)
在本实施方式中,也可以具备控制袋状构件的压力的压力控制机构。作为压力控制机构,例如图2所示,可举出压力控制阀52等。各袋状构件的压力可以通过与各袋状构件连接的压力控制阀52单独控制,也可以通过一个压力控制阀52统一控制。
(实验1)
在实验1中,说明实施方式1的效果。
在层压膜制的外装体中收纳了正极、隔膜和负极层叠而成的电极体。注入电解液后,将外装体密封,组装成锂离子二次电池的电池单元。另外,准备封入有压缩空气的袋状构件。
参照图2,在一对端板50a与50b之间,以在层叠电极体的层叠方向上施加约束压的方式,分别交替层叠5个电池单元100和6个袋状构件51。在各袋状构件51连接压力控制阀52,控制压力控制阀52以成为一定压力。
通过袋状构件51内的压缩空气的压力,对电池单元100施加约束压,在电池单元100被恒压约束的状态下进行初始充电直至达到初始充电电压。
通过采用上述结构,能够对电池单元100的电极均匀地施加约束压。另外,对于伴随初始充电的电池单元100的膨胀和收缩,袋状构件也能够吸收电池单元厚度的变化量。
[实施方式2]
实施方式2在还具备调节电池单元温度的温度调节机构这点上,与实施方式1不同。
例如,在通过使电池单元的温度尽可能均匀而获得排除了温度因素的电池特性的情况下,通过封入袋状构件中的流体冷却电池单元,由此能够排除因充放电引起的电池单元发热的影响。
作为温度调节机构,例如可举出冷却器(冷却水循环装置)等。
另外,也可以具备充放电停止机构,该充放电停止机构监视封入袋状构件中的流体温度,在流体温度超过阈值温度时停止充放电。
例如,初始充电时电池单元可能因异物等而短路,如果电池单元因短路而发热,则流体温度上升。因此,通过监视流体温度,可预见电池单元的短路。另外,通过具备停止充放电的充放电停止机构,在流体温度超过阈值温度时能够防止电池单元的发热。
(实验2)
在实验2中,说明实施方式2的效果。
代替压缩空气而将冷却水封入袋状构件,作为温度调节机构将冷却器与袋状构件连接,除此以外的结构与实验1相同。
通过采用上述结构,除了可得到与实验1同样的效果之外,还可降低用冷却水冷却电池单元而引起的电池单元间的温度不均。由此,能够实施稳定的初始充电。
[实施方式3]
实施方式3中,还具备流体放出机构,在电池单元的温度超过阈值温度的情况下,通过流体放出机构放出袋状构件内部的流体。实施方式3在这点上与实施方式1和2不同。
例如,初始充电时电池单元可能因异物等而短路。特别是在对高容量的电池单元初始充电时,电池单元的发热量可能变大。因此,通过具备将袋状构件内部的流体放出的流体放出机构,在电池单元的温度超过阈值温度的情况下,能够防止电池单元发热。
作为流体放出机构,例如可举出对袋状构件设置阀等。
(实验3)
在实验3中,说明实施方式3的效果。
在袋状构件上设置阀作为流体放出机构,除此以外的结构与实验2相同。
通过采用上述结构,除了可得到与实验1和2同样的效果之外,在电池单元发生温度异常时,袋状构件的阀被打开,该电池单元被冷却水冷却。由此,能够防止电池单元发热,高效地实施初始充电。
应该认为本次公开的实施方式和实施例在所有方面都是例示而不是限制性的。本公开的范围不是由上述说明表示,而是由权利要求的范围表示,包括与权利要求的范围均等的意思及范围内的所有变更。
Claims (4)
1.一种锂离子二次电池的制造方法,包含以下工序:
制作包含正极层、隔膜和负极层的电极体;
将所述电极体和电解液封入外装体从而组装电池单元;以及
使袋状构件和所述电池单元交替层叠,在沿着所述电池单元的层叠方向对所述电池单元进行恒压约束的状态下进行初始充电直至达到初始充电电压,
所述袋状构件在其内部密封有流体。
2.根据权利要求1所述的锂离子二次电池的制造方法,
还具备控制所述袋状构件的压力的压力控制机构。
3.根据权利要求1或2所述的锂离子二次电池的制造方法,
还具备调节所述电池单元的温度的温度调节机构。
4.根据权利要求1~3中任一项所述的锂离子二次电池的制造方法,
还具备流体放出机构,在所述电池单元的温度超过阈值温度的情况下,通过所述流体放出机构放出所述袋状构件的内部的流体。
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