CN107438909B - 用于二次电池的袋型壳体及包括该袋型壳体的袋型二次电池 - Google Patents
用于二次电池的袋型壳体及包括该袋型壳体的袋型二次电池 Download PDFInfo
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- CN107438909B CN107438909B CN201680005911.0A CN201680005911A CN107438909B CN 107438909 B CN107438909 B CN 107438909B CN 201680005911 A CN201680005911 A CN 201680005911A CN 107438909 B CN107438909 B CN 107438909B
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- secondary battery
- resin layer
- pouch
- type case
- moisture absorbent
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Abstract
本公开内容涉及一种用于二次电池的袋型壳体及包括该袋型壳体的二次电池，且具体地，涉及一种通过将内部树脂层、中间树脂层和外部树脂层进行层压制成的用于二次电池的袋型壳体及包括该袋型壳体的二次电池，其中所述内部树脂层包括聚烯烃基树脂和热固性吸湿剂。
Description
技术领域
与相关申请的相互引用
本申请要求于2015年3月31日在韩国知识产权局提交的韩国专利申请第10-2015-0045310号的优先权和权益，通过引用将上述专利申请的全部内容结合在此。
技术领域
本公开内容涉及一种袋型壳体及包括该袋型壳体的袋型二次电池，且具体地，涉及提供有湿气感测功能并且包括内部树脂层/中间树脂层/外部树脂层的袋型壳体及包括该袋型壳体的袋型二次电池。
背景技术
随着对移动装置的技术发展和需求增加，对作为能源的二次电池的需求迅速增长，并因此，展开了对能够响应于各种需求的二次电池的研究。
就二次电池的形状而言，对能够用在诸如手机之类的产品中的具有较小宽度的棱柱型锂二次电池和袋型锂二次电池的需求较高，就材料而言，对具有优异的能量密度、放电电压和安全性的锂钴聚合二次电池的需求较高。
相较于袋型锂二次电池，棱柱型锂二次电池有利于保护电极组件免受外部冲击，并且具有简单的电解质注入工艺，但因其形状固定而在减小体积方面存在缺点。因此，使用这种棱柱型锂二次电池作为电源的电子产品的缺点在于其设计受到限制。此外，就安全性而言，棱柱型锂二次电池具有以下缺点：不具有释放气体或液体的顺畅排放效果，因此，随着内部热量或气体积聚而具有较高的爆炸风险，并且由于未能释放出的热量而引起的过热而导致在较短时间间隔内引发电池劣化。
此外，袋型锂二次电池在形状和尺寸方面没有限制，很容易通过热粘合进行组装，并且在发生异常行为时具有良好的释放气体或液体的排放效果，从而比棱柱型二次电池具有高安全性的优点。因此，袋型二次电池特别适合于制造具有较小厚度的电池。然而，不同于棱柱型二次电池，袋型二次电池使用具有较小厚度的软袋作为壳体容器，因此，袋型二次电池具有以下缺点：较弱的物理和机械强度及低密封可靠性。
因此，已经扩展了针对开发在电池内部的电化学反应下甚至是在高温和高湿度的外部条件下稳定的袋型壳体的研究。
当观察袋型壳体的剖面时，如图1所示，所述袋型壳体包括：作为密封单元的内层11，其具有热粘合性能而因此起到密封剂的作用；金属层17，起到湿气和氧阻挡层的作用同时维持机械强度；以及外层19，用作基板保护层。
在此，即使当将袋型壳体中的盖单元的内层(密封单元)和存储单元的内层(密封单元)连接时，也难以确保二次电池的完全密封。具体地，在制造工艺期间，用于连接内层的诸如聚丙烯之类的粘合剂聚合物在高温和高湿度环境下往往对湿气渗透较弱，这导致盖单元和存储单元的连接单元之间的湿气渗透的问题。
二次电池使用将电解质和添加剂溶解在诸如碳酸酯之类的非水溶剂中的电解质溶液，并且作为电解质，通常使用在与导电金属等相互作用方面具有良好特性的氟基化合物。
当湿气渗入二次电池中时，电极组件、接片和壳体(金属层)的腐蚀加快，同时由于湿气导致氟化氢从氟化物中分离出来，并且电池性能可能劣化。此外，由湿气导致的各种副反应加快了电池的劣化和气体产生，这可能会导致二次电池的寿命减少和爆炸。
因此，需要能够通过在二次电池的制造过程中区分因湿气渗透而导致性能劣化的二次电池来制造可靠的二次电池的大规模生产方法。
发明内容
技术问题
综上所述，本发明提供一种具有湿气感测功能的用于二次电池的袋型壳体，以便在制造工艺期间感测和区分因湿气渗透而导致性能劣化的二次电池。
本发明提供一种包括所述用于二次电池的袋型壳体的袋型二次电池。
技术方案
本公开内容的一个实施方式提供一种通过将内部树脂层、中间树脂层和外部树脂层进行层压制成的用于二次电池的袋型壳体，其中所述内部树脂层包括聚烯烃基树脂和热固性吸湿剂。
在此，所述热固性吸湿剂(超吸收性聚合物；SAP)的典型实例可包括选自由丙烯酸酯基共聚物(其中诸如丙烯酸或丙烯酰胺的至少一个单体被接枝)、乙烯马来酸酐共聚物(ethylene maleic anhydride copolymer)、羧甲基纤维素(carboxyl methyl cellulose)和聚环氧乙烷(polyethylene oxide)构成的组中的至少一种。
所述热固性吸湿剂可以作为粘合剂聚合物的聚烯烃基树脂的总重量计，大约1重量％至5重量％的量被包括，并且可均匀地分散在聚烯烃基树脂中。
此外，可通过以下方法来制备所述内部树脂层：将所述热固性吸湿剂研磨以制备热固性吸湿剂粉末；制备聚烯烃基树脂溶液；将所述热固性吸湿剂粉末分散到所述聚烯烃基树脂溶液中；以及将分散有热固性吸湿剂粉末的聚烯烃基树脂溶液挤出以制备膜。
本公开内容的另一实施方式提供一种袋型二次电池，所述袋型二次电池包括电极组件；和容纳所述电极组件的本公开内容的所述袋型壳体。
有益效果
通过提供由包括聚烯烃基树脂和热固性吸湿剂的内部树脂层、中间树脂层和外部树脂层形成的用于二次电池的袋型壳体，本公开内容能够在二次电池的制造过程中感测和区分因湿气渗透而导致性能劣化的二次电池。结果，能够提高袋型二次电池的可靠性和产量。
附图说明
图1是示意性地示出了一般的袋型壳体的截面图。
图2是示意性地示出了根据本公开内容的一个实施方式的袋型壳体结构的截面图。
图3是示意性地示出了根据本公开内容的一个实施方式的在高温和高湿度环境下制造的袋型壳体的内部变化的截面图。
附图标记
11、21：内部树脂层
17：金属层
19、27：外部树脂层
23：吸湿前的热固性吸湿颗粒
23-1：吸湿后的热固性吸湿颗粒
25：中间树脂层。
具体实施方式
下文中，将更加详细地描述本发明，以帮助理解本发明。在此，本说明书和权利要求书中使用的术语或词语不应解释为受限于一般和字典意义，而是应基于发明人可适当地定义术语的概念的原则而解释为对应于本发明的技术构思的意义和概念，以便以可能的最佳方式描述本发明。
综上所述，本公开内容提供一种通过将内部树脂层、中间树脂层和外部树脂层进行层压制成的用于二次电池的袋型壳体，其中所述内部树脂层包括聚烯烃基树脂和热固性吸湿剂。
此外，本公开内容的一个实施方式包括电极组件；和容纳所述电极组件的本公开内容的所述袋型壳体。
下文中，将参照附图更加详细地描述本公开内容。
首先，根据本公开内容的一个实施方式的用于二次电池的袋型壳体包括如图2中所示的以下部件：作为密封单元的内部树脂层21，通过热粘合性能而起到密封剂的作用；中间树脂层25，通过阻挡湿气渗透和电荷传输而防止副反应，同时维持机械强度；以及外部树脂层27，用作保护层。
具体地说，所述内部树脂层包括作为主要成分的聚烯烃基树脂，即粘合剂聚合物，以便确保粘合性能。
聚烯烃基树脂的典型实例可包括选自由取向聚丙烯或流延聚丙烯(CastedPolypropylene，CPP)共聚物、聚乙烯共聚物、乙烯-丙烯共聚物、以及聚丙烯和丙烯酸的共聚物构成的组的至少一种。
具体地，在本公开内容的用于二次电池的袋型壳体中，所述内部树脂层可进一步包括热固性吸湿剂23，热固性吸湿剂23在吸附湿气时变成凝胶，体积增大，以便区分透湿性。
热固性吸湿剂(超吸收性聚合物；SAP)的典型实例可包括选自由丙烯酸酯基共聚物(其中诸如丙烯酸或丙烯酰胺的至少一个单体被接枝)、乙烯马来酸酐共聚物(ethylenemaleic anhydride copolymer)、羧甲基纤维素(carboxyl methyl cellulose)和聚环氧乙烷(polyethylene oxide)构成的组的至少一种。
热固性吸湿剂可以作为粘合剂聚合物的聚烯烃基树脂的总重量计，大约1重量％至5重量％的量被包括，并且可分散在聚烯烃基树脂中。
当所包括的热固性吸湿剂的量小于1重量％时，材料很难均匀地分散在全部聚烯烃基树脂中，并且也很难肉眼观察到吸湿程度，这导致感测湿气渗入袋型壳体的效果不显著。当所包括的热固性吸湿剂的量大于5重量％时，粘合剂聚合物产生的粘合强度减小，导致内部树脂层的结构弱化的缺点。
此外，热固性吸湿剂的平均颗粒直径优选为大约5μm以下。具体地，热固性吸湿剂能够吸附湿气而足以使重量增加至其初始重量的大约10倍以上。
在此，具有大于5μm的初始颗粒直径的热固性吸湿剂颗粒不是优选的，因为它会导致包括该吸附剂的层的厚度不均匀。
此外，参照图2时，热固性吸湿剂23是看不见的，因为这些颗粒的平均颗粒直径为大约5μm以下。然而，参照图3时，热固性吸湿剂23颗粒因吸附渗入袋的湿气而膨胀至10倍以上(23-1)，其尺寸增大至可以看见。因此，袋内的吸湿程度通过观察热固性吸湿剂颗粒的尺寸、袋型壳体的厚度变化等即为可见的，而无需复杂的测量方法。
此外，在本公开内容的袋型壳体中，可通过以下方法来制备所述内部树脂层：将热固性吸湿剂研磨以制备热固性吸湿剂粉末(步骤1)；
将所述热固性吸湿剂粉末分散到聚烯烃基树脂溶液中(步骤2)；以及
将分散有热固性吸湿剂粉末的聚烯烃基树脂溶液挤出以制备膜(步骤3)。
所述(步骤1)的研磨可使用剪切破裂干燥设备以1000rpm至5000rpm进行10分钟至30分钟。
所述(步骤2)的聚烯烃基树脂溶液可通过将聚烯烃基树脂熔融、或将聚烯烃基树脂溶解在诸如甲苯之类的溶剂中来制备。
在所述(步骤3)中，可通过将分散有热固性吸湿剂粉末的聚烯烃基树脂溶液挤出而制成具有大约20μm至100μm的厚度的内部树脂层。
在此，在本公开内容的袋型壳体中，内部树脂层的厚度优选为20μm至100μm。当内部树脂层的厚度大于100μm时，作为用于二次电池的袋型壳体，能量密度发生损失，当内部树脂层的厚度小于20μm时，难以实现密封层的作用，导致易使湿气渗透的问题。
如上所述，在形成本公开内容中的内部树脂层时，将热固性吸湿剂粉末分散到聚烯烃基树脂溶液中，然后将所得物挤出成膜，从而使热固性吸湿剂均匀地分布在内部树脂层中。
在本公开内容的袋型壳体中，可通过以下方式来制备中间树脂层：将诸如本领域中使用的铝之类的金属层挤出，或将具有优异的耐电解质特性的环烯烃基树脂层替代金属层挤出。
在此，环烯烃基树脂的典型实例可包括通过挤出降冰片烯基树脂、四环十二烷丙烯酸基树脂或类似树脂而制备的那些树脂。
在此，所述中间树脂层的厚度优选为60μm至100μm。
类似于内部树脂层，可通过以下方式来制备中间树脂层：将环烯烃基树脂层熔融或将环烯烃基树脂层溶解在溶剂中，将所得物挤出并成膜，然后将所得物施加或层压在内部树脂层上。
此外，在本公开内容的袋型壳体中，外部树脂层具体地可包括选自由聚乙烯、聚丙烯、聚对苯二甲酸乙二醇酯、尼龙、低密度聚乙烯(LDPE)、高密度聚乙烯(HDPE)和线性低密度聚乙烯(LLDPE)构成的组中的至少一个层。
外部树脂层的厚度可为10μm至100μm。
在本公开内容的袋型壳体中，可使用袋型壳体的制备中使用的常规方法将内部树脂层、中间树脂层和外部树脂层各自连接。具体地说，将内部树脂层、中间树脂层和外部树脂层的原材料各自熔融、挤出或铸造，并且依次层压成型以待制备，或者将各树脂原材料熔融、挤出或铸造以待制备成膜，然后进行热层压，或者可使用烯烃基粘合剂将各膜连接。
如上所述，在本公开内容中，用于二次电池的袋型壳体的内部树脂层包括在吸附湿气时变成凝胶的材料，因此，可提供能够区分透湿性的湿气渗透感测功能。因此，在袋型二次电池的制造中，籍由通过成形(forming)工艺来制备电池单元而进行循环测试时，可通过观察内部树脂层的凝胶化行为而感测和区分出因湿气渗透而性能劣化的二次电池，结果，可提高具有增强的可靠性的袋型二次电池的产量。
此外，本公开内容提供一种袋型二次电池，包括：电极组件；和容纳所述电极组件的本公开内容的所述袋型壳体。
在此，电极组件是通过隔离和卷绕包括负极活性材料的负极、包括正极活性材料的正极以及二者之间的隔板来制造的。
正极是通过以下方式制备的：将包括正极活性材料、导体和粘合剂的正极活性材料浆料涂覆在正极集电器上，然后将所得物干燥并收卷(rolling)。根据需要，可进一步将填料添加至正极活性材料浆料中。
在此，正极活性材料可与包括大多数锂插层材料(lithium intercalationmaterial)在内的化合物混合并使用，例如：层状化合物，诸如锂钴氧化物(LiCoO2)或锂镍氧化物(LiNiO2)或由至少一种过渡金属取代的化合物；诸如化学式为Li1+xMn2-xO4(在此，x为0至0.33)的锂锰化合物(LiMnO2)、LiMnO3、LiMn2O3和LiMnO2；锂铜氧化物(Li2CuO2)；钒氧化物，诸如LiV3O8、LiFe3O4、V2O5和Cu2V2O7；由化学式LiNi1-xMxO2(在此，M为Co、Mn、Al、Cu、Fe、Mg、B或Ga，且x为0.01至0.3)表示的锂镍氧化物；由化学式LiMn2-xMxO2(在此，M为Co、Ni、Fe、Cr、Zn或Ta，且x为0.01至0.1)或化学式Li2Mn3MO8(在此，M为Fe、Co、Ni、Cu或Zn)表示的锂锰复合氧化物；LiMn2O4，其中该化学式中的锂一部分被碱土金属所取代；二硫化合物；和由Fe2(MoO4)3制备的复合氧化物或它们的组合物。
正极集电器一般被制造成具有3μm至500μm的厚度。对这类正极集电器没有特别限制，只要其具有高导电性而且不会在相应电池中引起化学变化即可。例如，可使用不锈钢、铝、镍、钛、煅烧碳、或经碳、镍、钛、银等处理过表面的铝或不锈钢。集电器可通过在表面上制备细小的不平坦来增强正极活性材料的粘合强度，且可采用各种形式，诸如膜、片、箔、网、多孔体、泡沫和无纺布。
以包含正极活性材料的混合物的总重量计，导体一般添加的量为1重量％至50重量％。对这类导体没有特别限制，只要其具有导电性而且不会在相应电池中引起化学变化即可，导体的实例可包括：石墨，诸如天然石墨或人工石墨；炭黑，诸如乙炔黑、科琴黑、槽法炭黑、炉法炭黑、灯黑或热炭黑；导电纤维，诸如碳纤维或金属纤维；金属粉末，诸如氟化碳粉末、铝粉或镍粉；导电晶须，诸如氧化锌或钛酸钾；导电氧化物，诸如钛氧化物；导电材料，诸如聚苯撑的衍生物；和类似者。
粘合剂是有助于活性材料、导体等之间的结合以及有助于与集电器的结合的组分，并且相对于包含正极活性材料的混合物的总重量，粘合剂一般添加的量为1重量％至50重量％。这样的粘合剂的实例可包括聚偏二氟乙烯、聚乙烯醇、羧甲基纤维素(CMC)、淀粉、羟丙基纤维素、再生纤维素、聚乙烯吡咯烷酮、四氟乙烯、聚乙烯、聚丙烯、乙烯-丙烯-二烯三元聚合物(EPDM)、磺化的EPDM、丁苯橡胶、氟橡胶、各种共聚物和类似者。
填料是可根据需要使用的用于抑制正极膨胀的一种组分，对填料没有特别限制，只要是不会在相应电池中引起化学变化的纤维材料即可，填料的实例可包括：烯烃基聚合物，诸如聚乙烯或聚丙烯；或纤维材料，诸如玻璃纤维或碳纤维。
此外，负极是通过以下方式制备的：将包括负极活性材料、导体和粘合剂的负极活性材料浆料涂覆在负极集电器上，然后将所得物干燥并收卷。根据需要，可进一步将填料添加至负极活性材料浆料中。
负极集电器一般制造成具有3μm至500μm的厚度。对这类负极集电器没有特别限制，只要其具有导电性而且不会在相应电池中引起化学变化即可，负极集电器的实例可包括铜、不锈钢、铝、镍、钛、煅烧碳、或经碳、镍、钛、银等处理过表面的铜或不锈钢、铝镉合金或类似者。此外，类似于正极集电器，负极集电器可通过在表面上制备细小的不平坦来增强负极活性材料的粘合强度，且可采用各种形式，诸如膜、片、箔、网、多孔体、泡沫和无纺布。
负极材料包括无定型碳或者结晶碳，且具体而言，其可使用碳，诸如硬碳和石墨系碳；金属复合氧化物，诸如LixFe2O3(0≤x≤1)、LixWO2(0≤x≤1)、SnxMe1-xMe’yOz(Me：Mn、Fe、Pb、Ge；Me’：Al、B、P、Si、周期表中第1、2和3族的元素、卤素；0≤x≤1；1≤y≤3；1≤z≤8)；锂金属；锂合金；硅系合金；锡系合金；氧化物，诸如SnO、SnO2、PbO、PbO2、Pb2O3、Pb3O4、Sb2O3、Sb2O4、Sb2O5、GeO、GeO2、Bi2O3、Bi2O4或Bi2O5；导电聚合物，诸如聚乙炔；Li-Co-Ni系材料；和类似者。
此外，粘合剂需要对锂离子在电极中嵌入和脱出导致的电极活性材料的膨胀和收缩执行缓冲作用，因此，粘合剂优选地为具有弹性的聚合物。粘合剂包括通过水乳液聚合合成的橡胶基粘合剂。橡胶基粘合剂的典型实例可包括选自由丙烯腈橡胶、丁二烯橡胶和丁苯橡胶(SBR)构成的组中的至少一种。
隔板位于正极和负极之间并且使电极绝缘。隔板是众所周知的聚烯烃基隔板、在烯烃基基材上制备有机和无机复合层的复合隔板、或类似者。可无特别限制地使用隔板。
通过将集电器存储在袋型壳体中，并且将电解质溶液注入其中，从而制造出一电池。
根据本公开内容的电解质溶液为一种由非水电解质和锂所组成的含锂盐的非水电解质。作为非水电解质，可使用非水电解质溶液、固体电解质、无机固体电解质和类似者。
非水电解质溶液的实例可包括：非质子有机溶剂，诸如N-甲基-2-吡咯烷酮、碳酸丙烯酯、碳酸乙烯酯、碳酸丁烯酯、碳酸二甲酯、碳酸二乙酯、γ-丁内酯、1,2-二甲氧基乙烷、四氢呋喃、2-甲基四氢呋喃、二甲亚砜、1,3-二氧戊环、甲酰胺、二甲基甲酰胺、二氧戊环、乙腈、硝基甲烷、甲酸甲酯、乙酸甲酯、磷酸三酯、三甲氧基甲烷、二氧戊环衍生物、环丁砜、甲基环丁砜、1,3-二甲基-2-咪唑烷酮、碳酸丙烯酯衍生物、四氢呋喃衍生物、醚、丙酸甲酯和丙酸乙酯。
有机固体电解质的实例可包括：聚乙烯衍生物、聚环氧乙烷衍生物、聚环氧丙烷衍生物、磷酸酯聚合物、多聚赖氨酸、聚酯硫醚、聚乙烯醇、聚偏二氟乙烯、包括离子解离基团的聚合物和类似者。
无机固体电解质的实例可包括：锂的氮化物、卤化物、硫酸盐和类似物，诸如Li3N、LiI、Li5NI2、Li3N-LiI-LiOH、LiSiO4、LiSiO4-LiI-LiOH、Li2SiS3、Li4SiO4、Li4SiO4-LiI-LiOH和Li3PO4-Li2S-SiS2。
锂盐是易溶于非水电解质的一种材料，其实例可包括LiCl、LiBr、LiI、LiClO4、LiBF4、LiB10Cl10、LiPF6、LiCF3SO3、LiCF3CO2、LiAsF6、LiSbF6、LiAlCl4、CH3SO3Li、CF3SO3Li、(CF3SO2)2NLi、氯硼烷锂、低级脂族羧酸锂、4-苯基硼酸锂、酰亚胺和类似者。
此外，为了提高充电和放电特性、阻燃性和类似特性，可在非水电解质中添加以下化合物：诸如吡啶、亚磷酸三乙酯、三乙醇胺、环醚、乙二胺、n-乙二醇二甲醚(glyme)、六磷酸三酰胺、硝基苯衍生物、硫、醌亚胺染料、N-取代的恶唑烷酮、N,N-取代的咪唑烷、乙二醇二烷基醚、铵盐、吡咯、2-甲氧基乙醇和三氯化铝。在一些情况下，为了提供不燃性，可进一步包括含卤溶剂，诸如四氯化碳和三氟乙烯，并且为了提高高温储存特性，可进一步包含二氧化碳气体。
此外，这样的袋型二次电池优选为锂二次电池，但并不限于此。
本公开内容的袋型二次电池可用作大中型设备的电源的电池模组的单元电池。
实施例
实施例1
(内部树脂层的制备)
使用剪切破裂设备以3000rpm旋转将热固性吸湿剂羧甲基纤维素研磨20分钟，从而制备羧甲基纤维素粉末(平均颗粒直径：1μm)。
随后，将羧甲基纤维素粉末(3重量％)分散在聚丙烯树脂溶液中，然后将所得物在约220℃下挤出，从而制备具有40μm的厚度的内部树脂层。
(袋型壳体片的制备)
以层压的方式将厚度为60μm的降冰片烯树脂层压在所述内部树脂层上，从而制备中间树脂层。
接下来，将由15μm厚的尼龙组成的外部树脂层层压在所述中间树脂层上，以制造用于二次电池的袋型壳体。
实施例2
(内部树脂层的制备)
使用剪切破裂设备以3000rpm旋转将丙烯酸-丙烯酰胺共聚物研磨20分钟，从而制备丙烯酸-丙烯酰胺共聚物粉末(平均颗粒直径：1μm)。
随后，将丙烯酸-丙烯酰胺共聚物粉末(5重量％)分散在聚丙烯树脂溶液中，然后将所得物在约220℃下挤出，从而制备具有40μm的厚度的内部树脂层。
(袋型壳体片的制备)
以层压的方式将厚度为60μm的降冰片烯树脂层压在所述内部树脂层上，从而形成中间树脂层。
接下来，将由15μm厚的尼龙组成的外部树脂层层压在所述中间树脂层上，以制造用于二次电池的袋型壳体。
实施例3
使用剪切破裂设备以3000rpm旋转将乙烯-马来酸酐共聚物研磨20分钟，从而制备乙烯-马来酸酐共聚物粉末(平均颗粒直径：1μm)。
随后，将乙烯-马来酸酐共聚物粉末(1重量％)分散在聚丙烯和丙烯酸共聚物树脂溶液中，然后将所得物在约220℃下挤出并释放，从而制备具有40μm的厚度的内部树脂层。
(袋型壳体片的制备)
以层压的方式将厚度为60μm的降冰片烯树脂层压在所述内部树脂层上，从而制备中间树脂层。
接下来，将由15μm厚的尼龙形成的外部树脂层层压在所述中间树脂层上，以制造用于二次电池的袋型壳体。
比较实施例1
使用剪切破裂设备以3000rpm旋转将热固性吸湿剂羧甲基纤维素研磨20分钟，从而制备羧甲基纤维素粉末(平均颗粒直径：6μm)。
随后，将羧甲基纤维素粉末(5重量％)分散在聚丙烯树脂溶液中，然后将所得物在约220℃下挤出，从而制备具有40μm的厚度的内部树脂层。
(袋型壳体片的制备)
以层压的方式将厚度为60μm的降冰片烯树脂层压在所述内部树脂层上，从而制备中间树脂层。
接下来，将由15μm厚的尼龙组成的外部树脂层层压在所述中间树脂层上，以制造用于二次电池的袋型壳体。
比较实施例2
使用剪切破裂设备以3000rpm旋转将热固性吸湿剂羧甲基纤维素研磨20分钟，从而制备羧甲基纤维素粉末(平均颗粒直径：5μm)。
随后，将羧甲基纤维素粉末(6重量％)分散在聚丙烯树脂溶液中，然后将所得物在约220℃下挤出，从而制备具有40μm的厚度的内部树脂层。
(袋型壳体片的制备)
以层压的方式将厚度为60μm的降冰片烯树脂层压在所述内部树脂层上，从而制备中间树脂层。
接下来，将由15μm厚的尼龙组成的外部树脂层层压在所述中间树脂层上，以制造用于二次电池的袋型壳体。
比较实施例3
使用剪切破裂设备以3000rpm旋转将热固性吸湿剂羧甲基纤维素研磨20分钟，从而制备羧甲基纤维素粉末(平均颗粒直径：5μm)。
随后，将羧甲基纤维素粉末(5重量％)分散在聚丙烯树脂溶液中，然后将所得物在约220℃下挤出，从而制备具有110μm的厚度的内部树脂层。
(袋型壳体片的制备)
以层压的方式将厚度为60μm的降冰片烯树脂层压在所述内部树脂层上，从而制备中间树脂层。
接下来，将由15μm厚的尼龙组成的外部树脂层层压在所述中间树脂层上，以制造用于二次电池的袋型壳体。
试验实施例1
将实施例1至3和比较实施例1至3的袋型壳体片分别在湿度为90％的60℃烘箱中存储7天，然后对剖面进行鉴定。
在此，用肉眼观察实施例1至3和比较实施例1至3的各袋型壳体片内的热固性吸湿剂粉末的凝胶化。
然而，在比较实施例1的袋型壳体片中，可以看到袋内的热固性吸湿颗粒具有较大的颗粒直径，使得内部树脂层的厚度不均匀，导致袋型壳体的粘合强度下降。在比较实施例2的袋型壳体片中，可以看到由于袋内高含量的热固性吸湿颗粒而导致各树脂层之间的粘合强度下降。
此外，在比较实施例3的袋型壳体片中，虽然粘合强度增加，但由于内部树脂层的厚度导致二次电池的体积增大，并且能量密度可能发生损失。
根据上述结果，在制造二次电池时从视觉上可容易地感测和区分出因湿气渗透而性能劣化的二次电池。因此，可提高袋型二次电池的可靠性和产量。
Claims (11)
1.一种用于二次电池的袋型壳体，所述袋型壳体是通过将内部树脂层、中间树脂层和外部树脂层进行层压而制成的，
其中所述内部树脂层包括聚烯烃基树脂和热固性吸湿剂；
所述热固性吸湿剂以所述聚烯烃基树脂的总重量的1重量％至5重量％的量被包括；
所述热固性吸湿剂包括选自由丙烯酸酯基共聚物、乙烯马来酸酐共聚物、羧甲基纤维素和聚环氧乙烷构成的组中的至少一种；
所述热固性吸湿剂是具有1μm至5μm的颗粒直径的粉末；
所述热固性吸湿剂能够在二次电池的制造过程中因吸附渗入的湿气变成凝胶而膨胀至10倍以上，从而在二次电池的制造过程中区分出因湿气渗透而性能劣化的二次电池。
2.根据权利要求1所述的用于二次电池的袋型壳体，其中所述聚烯烃基树脂包括选自由取向聚丙烯或流延聚丙烯共聚物、聚乙烯共聚物、乙烯-丙烯共聚物、以及聚丙烯和丙烯酸的共聚物构成的组中的至少一种。
3.根据权利要求1所述的用于二次电池的袋型壳体，其中所述热固性吸湿剂分散在所述聚烯烃基树脂中。
4.根据权利要求1所述的用于二次电池的袋型壳体，其中所述内部树脂层是通过以下方法来制备：将所述热固性吸湿剂研磨以制备热固性吸湿剂粉末；将所述热固性吸湿剂粉末分散到聚烯烃基树脂溶液中；以及将分散有所述热固性吸湿剂粉末的聚烯烃基树脂溶液挤出以制备膜。
5.根据权利要求1所述的用于二次电池的袋型壳体，其中所述内部树脂层的厚度为20μm至100μm。
6.根据权利要求1所述的用于二次电池的袋型壳体，其中所述中间树脂层包括环烯烃基树脂。
7.根据权利要求1所述的用于二次电池的袋型壳体，其中所述中间树脂层的厚度为60μm至100μm。
8.根据权利要求1所述的用于二次电池的袋型壳体，其中所述外部树脂层包括选自由聚乙烯、聚丙烯、聚对苯二甲酸乙二醇酯、尼龙、低密度聚乙烯(LDPE)、高密度聚乙烯(HDPE)和线性低密度聚乙烯(LLDPE)构成的组中的至少一种。
9.根据权利要求1所述的用于二次电池的袋型壳体，其中所述外部树脂层的厚度为10μm至100μm。
10.一种袋型二次电池，包括：
电极组件；和
容纳所述电极组件的权利要求1所述的用于二次电池的袋型壳体。
11.根据权利要求10所述的袋型二次电池，其被用作大中型设备的电源的电池模组的单元电池。
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| US20020164441A1 (en) * | 2001-03-01 | 2002-11-07 | The University Of Chicago | Packaging for primary and secondary batteries |
| JP2004296174A (ja) * | 2003-03-26 | 2004-10-21 | Toppan Printing Co Ltd | リチウムイオン電池用外装材 |
| EP1747882A4 (en) | 2004-05-18 | 2010-11-17 | Gunze Kk | MULTI-LAYER THERMOSETTING FILM AND ROLL BATTERY |
| JP2007026682A (ja) * | 2005-07-12 | 2007-02-01 | Sony Corp | 非水電解質二次電池 |
| JP5092457B2 (ja) * | 2006-03-02 | 2012-12-05 | ソニー株式会社 | 電池素子外装材、これを用いた非水電解質二次電池及び電池パック |
| US8828591B2 (en) * | 2006-03-02 | 2014-09-09 | Sony Corporation | External packaging material for battery device, nonaqueous electrolyte secondary battery using the same, and battery pack |
| JP4849685B2 (ja) * | 2007-09-20 | 2012-01-11 | リケンテクノス株式会社 | 複合多層フィルム |
| CN101508368A (zh) | 2008-02-15 | 2009-08-19 | 艾尔坎技术及管理有限公司 | 用于泡罩基础部件的可冷成型层压材料 |
| JP5724952B2 (ja) * | 2012-06-11 | 2015-05-27 | トヨタ自動車株式会社 | 硫化物固体電池及びその製造方法 |
| KR101651141B1 (ko) | 2013-09-03 | 2016-08-25 | 주식회사 엘지화학 | 이차전지용 파우치 외장재 및 이를 포함하는 파우치형 이차전지 |
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2015
- 2015-03-31 KR KR1020150045310A patent/KR101821013B1/ko active IP Right Grant
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2016
- 2016-03-30 JP JP2017536866A patent/JP6518774B2/ja active Active
- 2016-03-30 US US15/542,513 patent/US10804507B2/en active Active
- 2016-03-30 PL PL16773443T patent/PL3279967T3/pl unknown
- 2016-03-30 WO PCT/KR2016/003276 patent/WO2016159662A1/ko active Application Filing
- 2016-03-30 CN CN201680005911.0A patent/CN107438909B/zh active Active
- 2016-03-30 EP EP16773443.3A patent/EP3279967B1/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| PL3279967T3 (pl) | 2019-07-31 |
| KR20160116906A (ko) | 2016-10-10 |
| WO2016159662A1 (ko) | 2016-10-06 |
| KR101821013B1 (ko) | 2018-01-22 |
| EP3279967B1 (en) | 2019-02-20 |
| US10804507B2 (en) | 2020-10-13 |
| JP2018503231A (ja) | 2018-02-01 |
| EP3279967A1 (en) | 2018-02-07 |
| JP6518774B2 (ja) | 2019-05-22 |
| CN107438909A (zh) | 2017-12-05 |
| EP3279967A4 (en) | 2018-02-14 |
| US20180269434A1 (en) | 2018-09-20 |
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