CN107017414A - 电池 - Google Patents
电池 Download PDFInfo
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- CN107017414A CN107017414A CN201611181575.3A CN201611181575A CN107017414A CN 107017414 A CN107017414 A CN 107017414A CN 201611181575 A CN201611181575 A CN 201611181575A CN 107017414 A CN107017414 A CN 107017414A
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- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical class [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 2
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Classifications
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- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Sealing Battery Cases Or Jackets (AREA)
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Abstract
本发明涉及包含至少正极集电体(8)、正极(2)、隔片(6)、电解质、负极(4)和负极集电体(10)的电池(1),正极(2)置于正极集电体(8)与隔片(6)之间,且负极(4)置于隔片(6)与负极集电体(10)之间,电池(1)进一步包含置于正极(2)、负极(4)和隔片(6)的周边并且将正极集电体(8)的内部边缘与负极集电体(10)的内部边缘连接的密封垫(12)。所述密封垫(12)至少部分地由粘弹性弹性体材料制成。
Description
发明领域
本发明涉及电池,所述电池包含至少正极(cathode)集电体、正极、隔片、电解质、负极(anode)和负极集电体,正极置于正极集电体与隔片之间,且负极置于隔片与负极集电体之间,电池进一步包含置于正极、负极和隔片的周边上并将正极集电体的内部边缘与负极集电体的内部边缘连接的密封垫。
发明背景
这类电池例如公开于专利EP 1202372中。它们优选呈薄膜的形式。为了在赋予明显机械应力的环境,例如手表手链、织物等中使用这些电池,需要开发非常挠性的电池。市场上可得到的电池不是足够挠性的,使得其在赋予明显机械应力的环境中的使用快速导致电池元件中的一个破裂。实际上,裂纹出现在包封材料中,例如在弯曲几次以后,导致电池的劣化。还开发了其中通常在电池末端找到的集电体用于包封的电池。因此,它是经受最高弯曲应力,即曲面的最大(外部)半径处的拉伸应力和在曲面的最小内部半径处的压缩应力的元件。因此,在小于约1.5cm的曲率半径处弯曲约100次以后,在集电体中出现裂纹。这些裂纹随着提高的弯曲而变得更加明显,并且形成折痕,其损害电池内部的活性层。这导致容量的降低变得日益明显并且最终破坏电池。
另外,除挠性外,电池还必须具有优异的气体屏障性能。实际上,锂离子电池的电活性材料例如对湿气非常敏感。
发明概述
本发明的目的是克服已知显示出不足挠性的电池的各种缺点。
更具体而言,本发明的目的是提供容许用于赋予明显机械应力的环境中的电池。
本发明的另一目的是提供提供其挠性与其气体屏障性能之间的折衷的电池。
为此,本发明涉及一种电池,所述电池包含至少正极集电体、正极、隔片、电解质、负极和负极集电体,正极置于正极集电体与隔片之间,且负极置于隔片与负极集电体之间,电池进一步包含置于正极、负极和隔片的周边并将正极集电体的内部边缘与负极集电体的内部边缘连接的密封垫。
根据本发明,所述密封垫至少部分地由粘弹性弹性体材料制成。优选,该粘弹性弹性体材料具有500Pa至100kPa的杨氏模量和250Pa至100kPa的剪切模量。
优选,电解质可以呈在水溶液中的盐的形式,使得电池的操作基于含水化学。
本发明电池显示出非常高的挠性,高于商业电池的挠性,又对气体,尤其是对空气湿气不敏感。
附图简述
本发明的其它特性和优点在阅读简单地通过说明性和非限定性实例给出的本发明一个实施方案的以下描述和附图时更清楚地显现,其中:
图1为本发明电池的截面图;
图2表示作为至多40个循环的循环数目的函数得到的电池容量,和
图3表示作为至多140个循环的循环数目的函数得到的电池容量。
优选实施方案详述
参考图1,显示本发明电池1。电池可以为可再充电或不可再充电的。本说明书中所用术语“电池”意指电池产品,以及电池单元或蓄电池。
电池1包含由隔片6彼此分离的正极2和负极4。电池1进一步包含两个集电体,即正极集电体8和负极集电体10。正极2置于正极集电体8与隔片6之间,且负极4置于隔片6与负极集电体10之间。
隔片6通常由聚合物或复合材料制成。
正极和负极集电体8和10可例如由不锈钢或者当要求极端挠性时由至少部分无定形金属材料制成。该无定形金属集电体描述于例如专利EP2795702中。
电池1进一步包含电解质用于正极2与负极4之间的离子交换。
另外,电池包含置于正极2、负极4和隔片6的周边以形成围绕这些元件的框架的不导电密封垫12。密封垫12置于正极集电体8与负极集电体10之间以将正极集电体8的内部边缘与负极集电体10的内部边缘连接。因此,密封垫12以及集电体8和10形成电池1的包封装置。
密封垫12的厚度等于正极、隔片和负极的厚度。通常,电池1具有约0.4mm的厚度,集电体8和10具有可从1μm至50μm变化的厚度。优选,厚度包含在5μm与30μm之间。
根据本发明,密封垫12至少部分地由粘弹性弹性体材料制成。有利地,该粘弹性弹性体材料不通过具有相当作用的另一方法硫化或交联。特别是,它不经受用硫硫化。优选,该粘弹性弹性体材料具有500Pa至100kPa的杨氏模量和250Pa至100kPa的剪切模量。优选,整个密封垫由该粘弹性弹性体材料制成。
由于本发明中所用材料的粘弹性,关于杨氏模量和剪切模量的这些值在应力开始时,分别在0-2%和0-1%下,以及在分别以10mm/min和2mm/min牵引中测量。
优选,本发明中所用粘弹性弹性体材料显示出多于50N/cm2(ASTM D-897,在72小时以后,50mm/min,6.45cm2,25℃)的拉伸强度和多于50N/cm2(ASTM D-1002,在72小时以后,12.7mm/min,6.45cm2,25℃)的动态抗剪强度。
杨氏模量和剪切模量值适于所需应用。特别是,对于要求非常大的挠性的应用如手表手链,从推荐的范围内选择低值。在这种情况下,弹性体材料可具有500Pa至3kPa的杨氏模量和250Pa至3kPa的剪切模量。来自推荐范围的高值可用于要求较低挠性的应用如信用卡中。
以特别有利的方式,本发明中所用弹性体材料可以为具有500-900kg/m3,优选600-800kg/m3的密度的泡沫。
密封垫可通过粘结,例如采用粘合剂组装到正极集电体8和负极集电体10的边缘,以便不削弱由弹性体材料提供的挠性。
以特别有利的方式,本发明中所用弹性体材料为压敏性或者自粘合粘合剂。这容许电池的简单、安全且快速包封。该材料也是自复原的。
优选,本发明中所用粘弹性弹性体材料选自包含丙烯酸类树脂、天然橡胶、丁基橡胶、硅橡胶、乙烯乙酸乙烯酯(EVA)、腈、苯乙烯嵌段共聚物(SBC)(例如苯乙烯-丁二烯-苯乙烯(SBS)、苯乙烯-乙烯/丁烯-苯乙烯(SEBS)、苯乙烯-乙烯/丙烯(SEP)和苯乙烯-异戊二烯-苯乙烯(SIS))和乙烯基醚的组。
优选,本发明中所用粘弹性弹性体材料为压敏粘合剂丙烯酸泡沫。
另外,选择本发明中所用粘弹性弹性体材料使得所述粘弹性弹性体材料与正极和负极集电体之间的粘合力大于所述粘弹性弹性体材料的内聚力。
也可通过将一个或另一个集电体的内表面活化而改进粘弹性弹性体材料在正极和负极集电体8和10的内部边缘上的附着力。可使用脱脂、磨蚀以使表面粗糙、等离子体/电晕处理、粘合底漆的沉积的已知技术。
粘弹性弹性体材料理想地通过辊对辊方法应用,其容许各个元件的精确排列、保护膜的容易脱除以及最后层粘附所需压力的施加。
本发明中所用粘弹性弹性体材料可吸收拉伸和压缩应力,使得两个正极和负极集电体可剪切。另外,剪切应力转变成正常拉伸/压缩应力,导致垫翘曲,这实际上消除了该应力对电池长度的依赖性。这意指可实现比曲面的半径长得多的电池。
因此,通过在具有0.4mm的总厚度的电池中使用2个具有25μm的厚度的完全无定形金属集电体,本发明电池可经得起至少5,000次以1cm的曲率半径弯曲而不损害后者。在目前市场上可得到的薄膜电池中,没有可幸免于以1cm的曲率半径弯曲150次的。
可选择本发明电池的元件以用在非水溶剂中的电解质或者固体电解质操作。这类化学惯常地用于电池中并且是本领域技术人员已知的。
然而,以特别优选和有利的方式,本发明电池中所用电解质呈在水溶液中的盐的形式,使得电池的操作基于含水化学。
在这种情况下,负极和正极有利地包含电位差在水稳定性的窗内的电活性材料。因此,不存在水氧化或还原形成氧气或氢气,这会导致电池的快速劣化。负极与正极之间的电压因此通常为约1.5V。
例如,电池元件使得电池为具有含水电解质的Ni-MH类型,或者在含水介质中的锂离子类型,例如(-)LISICON/LiNO3/LiMn2O4(+)。
电解质还可包含提高其电化学稳定性的添加剂。
有利地,电解质可通过弹性体垫注入以润湿所有电池元件。当材料为自复原的时,垫在注射以后再次闭合。
有利地,选择电解质盐浓度使得在正常使用条件下,电解质的饱和蒸气压等于电池位于其中的平均空气蒸气压(相对湿度),至±20%,优选±10%内。因此,如果环境空气变得比正常使用条件更干,则水从电池中蒸发,这具有使电解质浓缩并使平衡相对湿度转向较低值的作用。如果环境空气变得比正常使用条件更潮湿,则电池吸收水,这具有将电解质稀释并提高平衡相对湿度的作用。这些变化是可逆的,这确保长电池寿命。
因此,不同于其中任何水吸收是有害的非水电池,本发明含水电池可通过选择盐浓度以适于不同的环境空气条件而最佳化。除了得到非常高的挠性之外,本发明中所用弹性体密封垫也可吸收电池的体积变化,从而确保其合适操作而不管湿气条件。
本发明电池可用于各种应用,例如钟表应用或者智能卡或电话通信中的应用。
以下实施例阐述本发明而不由此限制其范围。
活性材料根据以下出版物合成:
-负极LiTi2(PO4)3:C.Wessells等人,J.Electrochem.Soc.,第158(3)卷,第A352页(2011)
-正极LiMn2O4:W.Liu等人,J.Electrochem.Soc.,第143(3)卷,第879页(1996),但将7.5摩尔%硝酸锰(II)用硝酸铬(III)代替。
电极的制备:
负极:复合物通过在行星式球磨机中以300rpm将LiTi2(PO4)3与炭黑(Super P)以1:1的比例研磨3小时而形成(20mm直径玛瑙球)。然后在玛瑙研钵中用8%PVDF(Kynar)和4%石墨(Timrex MX15)进行研磨,然后加入NMP,并继续研磨直至PVDF溶解并得到均匀分散体(约50%固体)。
正极:将LiCr0.15Mn1.85O4在玛瑙研钵中用8%PVDF(Kynar)和4%石墨(TimrexMX15)研磨,然后加入NMP,并继续研磨直至PVDF溶解并得到均匀分散体(约50%固体)。
负极和正极集电体为0.028mm厚的316L不锈钢片,将其用异丙醇脱脂并磨蚀以使表面粗糙化并改进附着力。然后将它们在意欲用于密封垫的位置(例如围绕电极5mm边沿)处用遮蔽胶带(例如Nitto PS-2)遮蔽,然后用先前的分散体使用棒和具有所需厚度如0.2mm的间隔物涂覆。
将电极在环境温度下干燥12小时,然后在100N/mm的压力下层压。
电池的组装:
将由3MTM出售,具有闭孔丙烯酸泡沫中心层,显示出如上所述测量为约2500Pa的杨氏模量和约300Pa的剪切模量且具有0.4mm的厚度的VHBTM粘合粘弹性弹性体胶带的条切成垫的所需尺寸(例如具有50mm×25mm的外部尺寸和40mm×15mm的内部尺寸的矩形框架)。
将该框架在遮蔽的位置处粘结在正极集电体上。
将玻璃微纤维隔片(Whatman GF/D)用电解质浸泡,所述电解质为还包含1%碳酸亚乙烯酯的Li2SO42M水溶液。
负极位于顶部,再次使得密封垫/框架在遮蔽的位置处粘附在钢集电体上。
施加20N/cm2的压力使得密封垫良好地粘附在钢上。
在储存1天以后,通过借助具有外径为约0.2mm的针的注射器(例如Hamilton HA-7750-22)将电解质注射通过密封垫而将电解质的体积补充至15μl/cm2。
图2表示作为循环数的函数得到的电池容量,其中循环1-19次的放电速率为1mA,然后在循环20次以后的放电速率为3mA。
图3表示以C/2放电40次(左边的第一部分曲线),其后以5C放电100次(右边的第二部分曲线),证明所得电池在100个循环以后的优异稳定性。
弯曲试验:
将根据本发明得到的电池夹在两个PET膜之间。将各个膜的一端固定在直径相当于所需曲率半径的2倍的圆筒上。将另一端固定在足以使电池弯曲,即将它挤压到圆筒上的500g平衡锤上。
然后将电池围绕圆筒辊压一定次数。通过在每次弯曲以后改变旋转方向,凸弯可与凹弯交替。
本发明电池可以以0.1Hz的频率以1cm的曲率半径交替弯曲5000次而不损坏。
Claims (12)
1.包含至少正极集电体(8)、正极(2)、隔片(6)、电解质、负极和负极集电体(10)的电池(1),正极(2)置于正极集电体(8)与隔片(6)之间,且负极(4)置于隔片(6)与负极集电体(10)之间,电池(1)进一步包含置于正极(2)、负极(4)和隔片(6)的周边并且将正极集电体(8)的内部边缘与负极集电体(10)的内部边缘连接的密封垫(12),其特征在于所述密封垫(12)至少部分地由粘弹性弹性体材料制成。
2.根据权利要求1的电池(1),其特征在于粘弹性弹性体材料具有500Pa至100kPa的杨氏模量和250Pa至100kPa的剪切模量。
3.根据权利要求2的电池(1),其特征在于粘弹性弹性体材料具有500Pa至3kPa的杨氏模量和250Pa至3kPa的剪切模量。
4.根据权利要求1的电池(1),其特征在于粘弹性弹性体材料为具有500-900kg/m3的密度的泡沫。
5.根据权利要求4的电池(1),其特征在于粘弹性弹性体材料为具有600-800kg/m3的密度的泡沫。
6.根据权利要求1的电池(1),其特征在于粘弹性弹性体材料为压敏粘合剂。
7.根据权利要求1的电池(1),其特征在于粘弹性弹性体材料选自包含丙烯酸类树脂、天然橡胶、丁基橡胶、硅橡胶、乙烯乙酸乙烯酯(EVA)、腈、苯乙烯嵌段共聚物(SBC)和乙烯基醚的组。
8.根据权利要求1的电池(1),其特征在于正极(8)和负极(10)集电体由至少部分无定形金属材料制成。
9.根据权利要求1的电池(1),其特征在于电解质呈水溶液中的盐的形式。
10.根据权利要求9的电池(1),其特征在于选择电解质盐浓度使得电解质的饱和蒸气压等于电池位于其中的平均空气蒸气压,至±20%内。
11.根据权利要求10的电池(1),其特征在于选择电解质浓度使得电解质的饱和蒸气压等于电池位于其中的平均空气蒸气压,至±10%内。
12.根据权利要求9的电池(1),其特征在于正极(2)和负极(4)有利地包含电位差在水稳定性的窗内的电活性材料。
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CN111819711A (zh) * | 2018-03-01 | 2020-10-23 | 美国亚德诺半导体公司 | 电池组件及其制造方法 |
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CN110534790A (zh) * | 2018-05-23 | 2019-12-03 | 松下知识产权经营株式会社 | 电池和层叠电池 |
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KR101898351B1 (ko) | 2018-09-12 |
EP3185335A1 (fr) | 2017-06-28 |
EP3185335B1 (fr) | 2020-02-05 |
US10056643B2 (en) | 2018-08-21 |
JP6364065B2 (ja) | 2018-07-25 |
US20170179517A1 (en) | 2017-06-22 |
JP2017117791A (ja) | 2017-06-29 |
KR20170074206A (ko) | 2017-06-29 |
CN107017414B (zh) | 2019-10-15 |
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