CN102687332B - 线缆型二次电池 - Google Patents

线缆型二次电池 Download PDF

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CN102687332B
CN102687332B CN201180004398.0A CN201180004398A CN102687332B CN 102687332 B CN102687332 B CN 102687332B CN 201180004398 A CN201180004398 A CN 201180004398A CN 102687332 B CN102687332 B CN 102687332B
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active material
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type rechargeable
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CN102687332A (zh
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权友涵
金帝映
吴丙薰
金奇泰
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LG Energy Solution Ltd
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Abstract

本发明提供一种线缆型二次电池，其包含：内电极，所述内电极包含平行配置的至少两个负极，所述负极纵向延伸并具有预定形状的水平横截面；电解质层，所述电解质层充当包围所述内电极的离子通道；外电极，所述外电极包含管状正极，所述管状正极具有预定形状的水平横截面并包围所述电解质层；以及包围所述外电极的保护涂层。所述线缆型二次电池因其线性和柔性而具有自由变形性。管状外电极内的多个内电极导致其间的接触面积增大并因此导致电池倍率高。通过调节内电极数可容易地控制所述内电极与外电极之间的容量平衡。

Description

线缆型二次电池
技术领域
本发明涉及变形自由的线缆型二次电池。
背景技术
本申请要求2010年2月1日在韩国提交的韩国专利申请10-2010-0009048的优先权，通过参考将其完整内容并入本文中。
此外，本申请要求2011年1月27日在韩国提交的申请10-2011-0008217号的优先权，通过参考将其完整内容并入本文中。
二次电池为能够以化学形式储存能量并在需要时将其转化成电能以发电的装置。所述二次电池也被称作可再充电电池，因为其能够反复再充电。普通的二次电池包括铅蓄电池、NiCd电池、NiMH蓄电池、Li离子电池、Li离子聚合物电池等。当与一次性的原电池相比时，二次电池不仅更加经济高效，而且更加环境友好。
目前将二次电池用于需要低电力的应用如用于帮助车辆启动的设备、便携式装置、工具、不间断电源等。近来，由于无线通信技术的开发导致便携式装置的普及并甚至导致多种常规装置的无线化，所以对二次电池的需求急剧增加。还将二次电池用于环境友好的下一代车辆如混合动力车辆和电动车辆中以降低成本和重量并提高车辆的使用寿命。
通常，二次电池具有圆柱形、棱柱形或袋形形状。这与二次电池的制造方法相关，在所述方法中，将由负极、正极和隔膜构成的电极组件安装在圆柱形或棱柱形金属壳或者铝层压片的袋形壳中，且在所述壳中填充有电解质。因为在这种方法中用于电极组件的预定安装空间是必需的，所以在开发多种形状的便携式装置时二次电池的圆柱形、棱柱形或袋形是一种限制。因此，需要形状变形容易的新结构的二次电池。
为了满足这种需要，已经建议开发长度对横截面的直径之比非常大的线性电池。韩国专利公开2005-0099903号公开了一种线型柔性电池，其包含内电极、电解质和外电极，但具有一个负极和一个正极的限制性结构并因此容量平衡低。韩国专利0804411公开了一种线性电池，所述线性电池包含多个负极和多个正极、以及插入到其间的隔膜。韩国专利注册0742739公开了一种包含正极线和负极线的线型柔性电池，然而，这不是以外电极/内电极结构为基础的。
发明内容
技术问题
本发明的目的是提供一种新型线性结构的二次电池，所述二次电池变形容易并具有优异的稳定性和性能。
技术方案
本发明的线缆型二次电池可包含内电极、电解质层、外电极、以及包围所述外电极的保护涂层，所述内电极包含平行配置的至少两个负极，所述负极纵向延伸并具有预定形状的水平横截面，所述电解质层充当包围所述内电极的离子通道，所述外电极包含管状正极，所述管状正极具有预定形状的水平横截面并包围所述电解质层。
此外，所述线缆型二次电池可包含内电极、电解质层、外电极、以及包围所述外电极的保护涂层，所述内电极包含平行配置的至少两个正极，所述正极纵向延伸并具有预定形状的水平横截面，所述电解质层充当包围所述内电极的离子通道，所述外电极包含具有管状负极，所述管状负极具有预定形状的水平横截面并包围所述电解质层。
所述负极或正极可具有圆形或多边形形状的横截面，其中所述圆形可以为几何对称的圆形形状或几何不对称的椭圆形形状，且所述多边形形状可以为三角形、方形、五边形或六边形形状。
优选地，所述负极或正极可包含集电器以及在所述集电器的表面上形成的活性材料层。
在这种情况下，所述集电器可优选由不锈钢、铝、镍、钛、烧结碳和铜；用碳、镍、钛和银进行表面处理的不锈钢；铝-镉合金；用导电材料进行表面处理的不导电聚合物；或导电聚合物制成。所述导电材料可包括聚乙炔、聚苯胺、聚吡咯、聚噻吩、聚氮化硫、铟锡氧化物(ITO)、银、钯、镍和铜。此外，所述导电聚合物可以包括聚乙炔、聚苯胺、聚吡咯、聚噻吩和聚氮化硫。
所述负极活性材料可以包括含碳材料；含锂的钛复合氧化物(LTO)；金属(Me)，包括Si、Sn、Li、Zn、Mg、Cd、Ce、Ni和Fe；金属(Me)的合金；金属(Me)的氧化物(MeOx)；金属(Me)和碳的复合材料。所述正极活性材料可包括LiCoO2、LiNiO2、LiMn2O4、LiCoPO4、LiFePO4、LiNiMnCoO2和LiNi1-x-y-zCoxM1yM2zO2(M1和M2各自独立地为选自Al、Ni、Co、Fe、Mn、V、Cr、Ti、W、Ta、Mg和Mo中的任一种，且x、y和z各自独立地为氧化物中各成分的原子分数，其中0≤x<0.5、0≤y<0.5、0≤z<0.5、x+y+z≤1)。
电解质层可由PEO、PVdF、PMMA、PAN或PVAc的胶凝聚合物电解质；或PEO、聚环氧丙烷(PPO)、聚乙烯亚胺(PEI)、聚乙烯硫化物(PES)或PVAc的固体电解质形成。
在本发明的线缆型二次电池中，所述电解质层可还包含锂盐。所述锂盐可包括LiCl、LiBr、LiI、LiClO4、LiBF4、LiB10Cl10、LiPF6、LiCF3SO3、LiCF3CO2、LiAsF6、LiSbF6、LiAlCl4、CH3SO3Li、CF3SO3Li、(CF3SO2)2NLi、氯硼烷锂、低级脂族碳酸锂和四苯基硼酸锂。
发明效果
本发明的线缆型二次电池因其线性和柔性而具有自由变形性，并由此可适用于各种便携式装置中，其中在所述线缆型二次电池中多个电极包含在另一个电极中。此外，所述电池具有多个内电极和管状外电极，这导致其间的接触面积增大并因此导致电池倍率高，且通过调节内电极数，更容易地控制了其间的容量平衡。通过存在多个内电极，可防止因重复使用而造成的短路。
根据下列详细说明、附图和权利要求书，其他特征和方面可变得显而易见。
附图说明
附图显示了本发明的优选实施方案，且所述附图与上述公开内容一起用于提供本发明技术主旨的进一步理解。然而，本发明不应被理解为限于所述附图。
图1是圆形线缆型二次电池的横截面图。
图2是椭圆形线缆型二次电池的横截面图。
附图标记说明
10：内电极的集电器        11：内电极的活性材料层
20：外电极的集电器        21：外电极的活性材料层
30：电解质层              40：保护涂层
具体实施方式
提供下列详细说明以帮助读者全面理解本文中所述的方法、设备和/或系统。因此，将对本领域中的技术人员提出本文中所述的系统、设备和/或方法的各种改变、变化和等价物。此外，为了更加清晰和简明，可省略熟知功能和构造的描述。
图1和2显示了根据本发明的线缆型二次电池的实例，其中将相同的元件表示为相同的标号。参考图1和2，本发明的线缆型二次电池包含内电极、电解质层30、外电极和保护涂层40。所述内电极包含平行配置的至少两个负极10和11，所述负极纵向延伸并具有预定形状的水平横截面。所述电解质层30包围所述内电极并充当离子通道。所述外电极包含管状正极20和21，所述管状正极20和21包围所述电解质层30并具有预定形状的水平横截面。所述保护涂层40包围所述外电极。此处，预定形状不限于特定形状，且在不背离本发明主旨和范围的条件下可包括任何形状。
本发明的线缆型二次电池具有预定形状的水平横截面和垂直于所述水平横截面延伸的线性结构。此外，所述线缆型二次电池具有柔性并因此可自由变形。所述线缆型二次电池可具有各种形状，例如图1中所示的几何对称的圆形形状或图2中所示的几何不对称的椭圆形形状。
本发明的线缆型二次电池具有包含多个负极的内电极和包含管状正极的外电极。所述负极或正极通常包含集电器和在所述集电器上形成的活性材料层。然而，当活性材料层独自充当集电器时，可不需要集电器。所述负极或正极可具有圆形或多边形形状的横截面，其中所述圆形形状可以为几何对称的圆形形状或几何不对称的椭圆形形状，且所述多边形形状不限于特定类型的多边形，只要不是二维的片型即可。例如，所述多边形可以为但不限于，三角形、方形、五边形或六边形形状。
所述内电极包含平行配置的至少两个负极，然而，在这点上本发明不受限制。例如，可以以直的或扭曲的形状配置多个负极。在图1中，显示了包含三个负极的内电极，在图2中显示了包含两个负极的内电极。
包含多个电极的线缆型二次电池，因为与相对电极的接触面积增大而具有高电池倍率和优异的单电池性能。此外，所述线缆型二次电池可能因其柔性而经历由重复使用所造成的短路，然而，即使当在一个电极中发生短路时，所述电池仍可工作。为了保持电池的容量平衡，与包含正极的内电极中所使用的正极活性材料相比，包含负极的内电极应使用更大量的负极活性材料，这是因为负极活性材料比正极活性材料具有更高的单位体积的容量的事实。在本发明中，通过调节内电极数，可控制内电极与外电极之间的容量平衡。
优选地，本发明的负极或正极包含集电器10或20以及通过涂布而在所述集电器10或20的表面上形成的活性材料层11或21。所述活性材料使得离子可通过集电器10或20发生迁移，并通过离子的嵌入/脱嵌而进入/离开电解质层30来实施离子迁移。
优选地，所述集电器10或20可由不锈钢、铝、镍、钛、烧结碳和铜；用碳、镍、钛和银进行表面处理的不锈钢；铝-镉合金；用导电材料进行表面处理的不导电聚合物；或导电聚合物制成。
所述集电器10或20收集由活性材料的电化学反应所产生的电子，或供应电化学反应所需要的电子。通常，集电器10或20由金属如铜或铝制成。然而，当集电器10或20特别地为用导电材料进行表面处理的不导电聚合物或导电聚合物的聚合物导体时，与集电器10或20由金属如铜或铝制成的情况相比，柔性相对更高。由于本发明的线缆型二次电池可具有多个电极，所以可使用多个集电器。因此，即使各个集电器的柔性发生小变化也会影响整个电池的柔性。此外，利用聚合物集电器代替金属集电器可使得电池的重量减轻。
所述导电材料可包括聚乙炔、聚苯胺、聚吡咯、聚噻吩、聚氮化硫、铟锡氧化物(ITO)、银、钯、镍和铜。所述导电聚合物可包括聚乙炔、聚苯胺、聚吡咯、聚噻吩和聚氮化硫。然而，用于集电器10或20的不导电聚合物不限于特定类型的不导电聚合物。
所述负极活性材料可包括但不限于，含碳材料；含锂的钛复合氧化物(LTO)；金属(Me)，包括Si、Sn、Li、Zn、Mg、Cd、Ce、Ni和Fe；金属(Me)的合金；金属(Me)的氧化物(MeOx)；以及金属(Me)和碳的复合材料。
所述正极活性材料可包括但不限于，LiCoO2、LiNiO2、LiMn2O4、LiCoPO4、LiFePO4、LiNiMnCoO2和LiNi1-x-y-zCoxM1yM2zO2(M1和M2各自独立地为选自Al、Ni、Co、Fe、Mn、V、Cr、Ti、W、Ta、Mg和Mo中的任一种，且x、y和z各自独立地为氧化物中各成分的原子分数，其中0≤x<0.5、0≤y<0.5、0≤z<0.5、x+y+z≤1)。
在本发明的线缆型二次电池中，包围内电极的电解质层30充当离子通道并由聚环氧乙烷(PEO)、聚偏二氟乙烯(PVdF)、聚甲基丙烯酸甲酯(PMMA)、聚丙烯腈(PAN)或聚乙酸乙烯酯(PVAc)的胶凝聚合物电解质；或PEO、聚环氧丙烷(PPO)、聚乙烯亚胺(PEI)、聚乙烯硫化物(PES)或PVAc的固体电解质制成。优选地，所述固体电解质的基体基本为聚合物基体或陶瓷-玻璃基体。即使典型的聚合物电解质具有充分的离子传导率，离子仍可能移动缓慢，即反应速度仍可能低，由此优选与固体电解质相比，具有有利的离子移动的胶凝聚合物电解质。因为胶凝聚合物电解质的机械性能差，所以可使用多孔载体或交联的聚合物以提高胶凝聚合物电解质的机械性能。本发明的电解质层30可充当隔膜，由此可不使用隔膜。
本发明的电解质层30可还包含锂盐。所述锂盐可提高离子传导率和反应速度，且可包括但不限于，例如LiCl、LiBr、LiI、LiClO4、LiBF4、LiB10Cl10、LiPF6、LiCF3SO3、LiCF3CO2、LiAsF6、LiSbF6、LiAlCl4、CH3SO3Li、CF3SO3Li、(CF3SO2)2NLi、氯硼烷锂、低级脂族碳酸锂和四苯基硼酸锂。
本发明的保护涂层40充当绝缘体，且为了防止电极受空气中的水分或外部冲击影响而形成在外电极的外表面上。所述保护涂层40可包括典型的聚合物树脂如PVC、高密度聚乙烯(HDPE)或环氧树脂。
此外，本发明的线缆型二次电池可包含内电极(正极)和外电极(负极)。即，本发明的线缆型二次电池可包含内电极、电解质层30、外电极和保护涂层40。所述内电极包含平行配置的至少两个正极10和11，所述正极纵向延伸并具有预定形状的水平横截面。所述电解质层30包围所述内电极并充当离子通道。所述外电极包含管状负极20和21，所述管状负极20和21包围所述电解质层30并具有预定形状的水平横截面。所述保护涂层40包围所述外电极。用于正极、负极、电解质层和保护涂层的成分可以为上述成分。
在下文中，将在下面简单地对制造如上所述的线缆型二次电池的方法进行说明。
负极或正极具有通过涂布而在集电器10或20上形成的活性材料层11或21。在这种情况下，可使用典型的涂布方法，具体地为电镀法或阳极氧化法。优选通过挤出机在集电器上挤出涂布包含活性材料的电极浆体。
在将形成的负极或正极用作内电极之后，在内电极周围形成电解质层30。或者，可将内电极插入电解质层30中。在形成内电极和电解质层30之后，在其上形成外电极和保护涂层40。或者，在形成电解质层30、外电极和保护涂层40之后，可以将内电极插入到电解质层30中，或在形成外电极和保护涂层40之后，可以插入内电极并然后可以形成电解质层30。

Claims (13)

1.一种线缆型二次电池，其包含：
内电极，所述内电极包含平行配置的至少两个负极，所述负极纵向延伸并具有预定形状的水平横截面；
电解质层，所述电解质层包围所述内电极并充当离子通道；
外电极，所述外电极包含管状正极，所述管状正极具有预定形状的水平横截面并包围所述电解质层；以及
包围所述外电极的保护涂层，
其中所述负极包含集电器以及在所述集电器的外表面上形成的负极活性材料层，
其中所述正极包含集电器以及在所述集电器的内侧上形成的正极活性材料层，
其中所述负极活性材料层由活性材料形成，所述活性材料包含选自如下物质中的任一种或它们的混合物的活性材料粒子：含碳材料；含锂的钛复合氧化物LTO；金属Me，包括Si、Sn、Li、Zn、Mg、Cd、Ce、Ni和Fe；所述金属Me的合金；所述金属Me的氧化物MeOx；以及所述金属Me与碳的复合材料，
其中所述正极活性材料层由活性材料形成，所述活性材料包含选自如下物质中的任一种或它们的混合物的活性材料粒子：LiCoO2、LiNiO2、LiMn2O4、LiCoPO4、LiFePO4、LiNiMnCoO2和LiNi1-x-y-zCoxM1yM2zO2，其中M1和M2各自独立地为选自Al、Ni、Co、Fe、Mn、V、Cr、Ti、W、Ta、Mg和Mo中的任一种，且x、y和z各自独立地为氧化物中各成分的原子分数，其中0≤x<0.5，0≤y<0.5，0≤z<0.5，x+y+z≤1。
2.一种线缆型二次电池，其包含：
内电极，所述内电极包含平行配置的至少两个正极，所述正极纵向延伸并具有预定形状的水平横截面；
电解质层，所述电解质层包围所述内电极并充当离子通道；
外电极，所述外电极包含管状负极，所述管状负极具有预定形状的水平横截面并包围所述电解质层；以及
包围所述外电极的保护涂层，
其中所述正极包含集电器以及在所述集电器的外表面上形成的正极活性材料层，
其中所述负极包含集电器以及在所述集电器的内侧上形成的负极活性材料层，
其中所述负极活性材料层由活性材料形成，所述活性材料包含选自如下物质中的任一种或它们的混合物的活性材料粒子：含碳材料；含锂的钛复合氧化物LTO；金属Me，包括Si、Sn、Li、Zn、Mg、Cd、Ce、Ni和Fe；所述金属Me的合金；所述金属Me的氧化物MeOx；以及所述金属Me与碳的复合材料，
其中所述正极活性材料层由活性材料形成，所述活性材料包含选自如下物质中的任一种或它们的混合物的活性材料粒子：LiCoO2、LiNiO2、LiMn2O4、LiCoPO4、LiFePO4、LiNiMnCoO2和LiNi1-x-y-zCoxM1yM2zO2，其中M1和M2各自独立地为选自Al、Ni、Co、Fe、Mn、V、Cr、Ti、W、Ta、Mg和Mo中的任一种，且x、y和z各自独立地为氧化物中各成分的原子分数，其中0≤x<0.5，0≤y<0.5，0≤z<0.5，x+y+z≤1。
3.如权利要求1或2所述的线缆型二次电池，其中所述负极具有圆形或多边形形状的横截面。
4.如权利要求1或2所述的线缆型二次电池，其中所述正极具有圆形或多边形形状的横截面。
5.如权利要求1所述的线缆型二次电池，其中所述集电器由如下材料制成：不锈钢、铝、镍、钛、烧结碳和铜；用碳、镍、钛和银进行表面处理的不锈钢；铝-镉合金；用导电材料进行表面处理的不导电聚合物；或导电聚合物。
6.如权利要求5所述的线缆型二次电池，其中所述导电材料为选自如下物质中的任一种或它们的混合物：聚乙炔、聚苯胺、聚吡咯、聚噻吩、聚氮化硫、铟锡氧化物ITO、银、钯、镍和铜。
7.如权利要求5所述的线缆型二次电池，其中所述导电聚合物为选自如下物质中的任一种或它们的混合物：聚乙炔、聚苯胺、聚吡咯、聚噻吩和聚氮化硫。
8.如权利要求1所述的线缆型二次电池，其中所述集电器由如下材料制成：不锈钢、铝、镍、钛、烧结碳和铜；用碳、镍、钛和银进行表面处理的不锈钢；铝-镉合金；用导电材料进行表面处理的不导电聚合物；或导电聚合物。
9.如权利要求8所述的线缆型二次电池，其中所述导电材料为选自如下物质中的任一种或它们的混合物：聚乙炔、聚苯胺、聚吡咯、聚噻吩、聚氮化硫、铟锡氧化物ITO、银、钯、镍和铜。
10.如权利要求8所述的线缆型二次电池，其中所述导电聚合物为选自如下物质中的任一种或它们的混合物：聚乙炔、聚苯胺、聚吡咯、聚噻吩和聚氮化硫。
11.如权利要求1或2所述的线缆型二次电池，其中所述电解质层由电解质形成，所述电解质选自：
PEO、PVdF、PMMA、PAN或PVAc的胶凝聚合物电解质；以及
PEO、聚环氧丙烷PPO、聚乙烯亚胺PEI、聚乙烯硫化物PES或PVAc的固体电解质。
12.如权利要求1或2所述的线缆型二次电池，其中所述电解质层还包含锂盐。
13.如权利要求12所述的线缆型二次电池，其中所述锂盐为选自如下物质中的任一种或它们的混合物：LiCl、LiBr、LiI、LiClO4、LiBF4、LiB10Cl10、LiPF6、LiCF3SO3、LiCF3CO2、LiAsF6、LiSbF6、LiAlCl4、CH3SO3Li、CF3SO3Li、(CF3SO2)2NLi、氯硼烷锂、低级脂族碳酸锂和四苯基硼酸锂。
CN201180004398.0A 2010-02-01 2011-01-27 线缆型二次电池 Active CN102687332B (zh)

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CN102687332A (zh) 2012-09-19
US9343773B2 (en) 2016-05-17
EP2533340A2 (en) 2012-12-12
KR20110089819A (ko) 2011-08-09
EP2533340B1 (en) 2018-12-05
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EP2533340A4 (en) 2014-04-16
US20120015233A1 (en) 2012-01-19

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