CN102598386B - 线缆型二次电池 - Google Patents
线缆型二次电池 Download PDFInfo
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- CN102598386B CN102598386B CN201180004395.7A CN201180004395A CN102598386B CN 102598386 B CN102598386 B CN 102598386B CN 201180004395 A CN201180004395 A CN 201180004395A CN 102598386 B CN102598386 B CN 102598386B
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- 239000011149 active material Substances 0.000 claims description 16
- 229910052759 nickel Inorganic materials 0.000 claims description 15
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- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 3
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Inorganic materials [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 claims description 3
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- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
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Abstract
本发明提供了一种线缆型二次电池,其包含:至少一个负极,其纵向延伸并具有预定形状的水平横截面;第一电解质层,其包围所述负极并充当离子通道;至少一个正极,其纵向延伸并具有预定形状的水平横截面,所述负极和所述正极平行配置;第二电解质层,其充当包围所述负极和所述正极两者的离子通道;和保护涂层,其包围所述第二电解质层。所述线缆型二次电池因其线性和柔性而具有自由变形性。电极上的电解质层的引入防止了短路。多个电极的存在导致其间的接触面积增大并因此导致电池倍率高。通过调节负极和正极的数目,可容易地控制其间的容量平衡。
Description
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
本申请要求于2010年2月1日在韩国提交的韩国专利申请10-2010-0009050的优先权,通过参考将其全部内容并入本文中。
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。
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。韩国专利申请公开2005-0099903公开了一种线型柔性电池,所述线型柔性电池包含内电极、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,该电池不进一步包含电解质层。
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以包含至少一个负极,其纵向延伸并具有预定形状的水平横截面;第一电解质层,其包围所述负极并充当离子通道;至少一个正极,其纵向延伸并具有预定形状的水平横截面,所述负极和所述正极平行配置;第二电解质层,其充当包围所述负极和所述正极两者的离子通道;和保护涂层,其包围所述第二电解质层。
此外,所述线缆型二次电池可以包含至少一个正极,其纵向延伸并具有预定形状的水平横截面;第一电解质层,其包围所述正极并充当离子通道;至少一个负极,其纵向延伸并具有预定形状的水平横截面,所述负极和所述正极平行配置;第二电解质层,其充当包围所述负极和所述正极两者的离子通道;和保护涂层,其包围所述第二电解质层。
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)。
所述第一电解质层和第二电解质层可以由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,所述第一电解质层和第二电解质层可还包含锂盐。所述锂盐可以包括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,并由此适用于各种便携式装置中。此外,所述电池具有通过涂布而形成在电极上的电解质层,从而防止电极之间的直接接触而消除了短路的可能性,并导致相对增加的表面积而实现高的电池倍率。此外,所述电池具有多个负极和多个正极,这导致其间的接触面积增大并因此导致电池倍率高,且通过调节负极和正极的数目,更易于控制其间的容量平衡。多个电极的存在可以防止由重复使用而造成的短路。
附图说明
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。除非另有说明,否则在附图和详细说明各处中,相同的附图标记应被理解为指示相同的元件、特征和结构。为了清晰、说明和方便,可以将这些元件的相关尺寸和描绘放大。
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:集电器 11:活性材料层
20:集电器 21:活性材料层
31:第一电解质层 32:第二电解质层
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至少一个负极10和11,其沿纵向延伸并具有预定形状的水平横截面;第一电解质层31,其包围所述负极并充当离子通道;至少一个正极20和21,其纵向延伸并具有预定形状的水平横截面;第二电解质层32,其充当包围所述负极和所述正极两者的离子通道;以及保护涂层40,其包围所述第二电解质层32。所述负极与所述正极平行配置。所述线缆型二次电池可还包含所述正极20和21上的电解质层。
或者,本发明的线缆型二次电池可以包含至少一个正极10和11,其纵向延伸并具有预定形状的水平横截面;第一电解质层31,其包围所述正极并充当离子通道;至少一个负极20和21,其纵向延伸并具有预定形状的水平横截面;第二电解质层,其充当包围所述负极和所述正极两者的离子通道;以及保护涂层40,其包围所述第二电解质层32。所述负极和所述正极平行配置。所述线缆型二次电池可还包含在所述负极20和21上的电解质层。在本文中,预定形状不限于特定形状,且可以包括任何不背离本发明主旨和范围的形状。
本发明的线缆型二次电池具有预定形状的水平横截面以及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具有自由变形性。所述线缆型二次电池可以具有各种形状诸如例如图1中所示的几何对称的圆形,或者图2中所示的几何不对称的椭圆形。
在本发明的线缆型二次电池中,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。
本发明的特征在于用于防止电极之间的直接接触,从而防止短路的负极和正极的至少一种上的第一电解质层31。第二电解质层32也防止短路,然而,由于反复使用所造成的破裂或者制造过程中的问题,仍然存在电极之间的直接接触的可能性。第一电解质层31的引入可以防止由直接接触所造成的短路。第二电解质层32包围平行配置的多个负极和多个正极,然而本发明在这点上不受限制。例如,当多个负极和多个正极发生绞合时,第二电解质层32也可以适用。第一电解质层和第二电解质层31和32可以由聚环氧乙烷(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的固体电解质形成。
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。
本发明的第一电解质层和第二电解质层31和32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。
如图1和图2所示,本发明的线缆型二次电池可以包含多个电极。在图1中,所示的电池包含九个电极,且在图2中,所示的电池包含五个电极。由于增加了与相对电极的接触面积,所以多个电极的存在实现了高的电池倍率和优异的电池性能。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,与正极活性材料相比,所述电池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,可以通过调节负极和正极的数目来控制调节负极与正极之间的容量平衡。
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31和32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实现电池的重量下降。
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)。
本发明的保护涂层40充当绝缘体,且形成在外电极的外表面上以保护电极不受空气中的水分或外部冲击影响。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。
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。
负极或者正极具有通过涂布而形成在集电器10或20上的活性材料层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。
围绕负极或者正极形成第一电解质层31。围绕负极和正极两者形成第二电解质层32。或者,可以将负极和正极插入到第二电解质层32中。围绕第二电解质层32形成保护涂层40。或者,在形成第二电解质层32和保护涂层40之后,可以将负极和正极插入到第二电解质层32中。
Claims (14)
1.一种线缆型二次电池,其包含:
至少一个负极,其纵向延伸并具有预定形状的水平横截面;
第一电解质层,其包围所述负极并充当离子通道;
至少一个正极,其纵向延伸并具有预定形状的水平横截面,所述负极和所述正极平行配置;
第二电解质层,其充当包围并接触所述第一电解质层和所述正极两者的离子通道;以及
保护涂层,其包围所述第二电解质层,
其中所述负极包含集电器和在所述集电器的外表面上形成的负极活性材料层,
所述正极包含集电器和在所述集电器的外侧上形成的正极活性材料层。
2.如权利要求1所述的线缆型二次电池,还包含:包围所述正极的电解质层。
3.一种线缆型二次电池,其包含:
至少一个正极,其纵向延伸并具有预定形状的水平横截面;
第一电解质层,其包围所述正极并充当离子通道;
至少一个负极,其纵向延伸并具有预定形状的水平横截面,所述负极和所述正极平行配置;
第二电解质层,其充当包围并接触所述负极和所述第一电解质层两者的离子通道;以及
保护涂层,其包围所述第二电解质层,
其中所述负极包含集电器和在所述集电器的外表面上形成的负极活性材料层,
所述正极包含集电器和在所述集电器的外侧上形成的正极活性材料层。
4.如权利要求3所述的线缆型二次电池,还包含:包围所述负极的电解质层。
5.如权利要求1至4中任一项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。
6.如权利要求1至4中任一项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。
7.如权利要求1所述的线缆型二次电池,其中所述正极集电器和负极集电器各自独立地由如下材料制成: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。
8.如权利要求7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。
9.如权利要求7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。
10.如权利要求1所述的线缆型二次电池,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。
11.如权利要求1所述的线缆型二次电池,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(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)。
12.如权利要求1至4中任一项所述的线缆型二次电池,其中所述第一电解质层和第二电解质层各自独立地由电解质形成,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。
13.如权利要求1至4中任一项所述的线缆型二次电池,其中所述第一电解质层和第二电解质层各自独立地还包含锂盐。
14.如权利要求13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。
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