CN104603971A - 二次电池用袋外饰材料及包含它的袋形二次电池 - Google Patents
二次电池用袋外饰材料及包含它的袋形二次电池 Download PDFInfo
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- CN104603971A CN104603971A CN201480001905.9A CN201480001905A CN104603971A CN 104603971 A CN104603971 A CN 104603971A CN 201480001905 A CN201480001905 A CN 201480001905A CN 104603971 A CN104603971 A CN 104603971A
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- resin layer
- exterior material
- outer exterior
- bag
- bag according
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Abstract
本发明涉及电池的袋外饰材料及包含它的二次电池，具体地，电池的袋外饰材料的特征在于由内部树脂层、中间树脂层及外部树脂层层叠而成的电池的袋外饰材料及包含它的二次电池。
Description
技术领域
本发明涉及二次电池用袋外饰材料及包含它的袋形二次电池，具体地，涉及用于在充放电过程中防止因袋外饰材料的腐蚀而使水分渗透，导致电池性能降低的由内部树脂层/中间树脂层/外部树脂层构成的多层袋外饰材料及包含它的袋形二次电池。
背景技术
最近，随着实现电子设备的小型化及轻量化，实现了便携式小型电子设备的常用化，对作为它们的电源的锂二次电池的需求正急剧增加。锂二次电池使用有机电解液，从而与以往使用碱水溶液的电池相比，呈现出两倍以上的高的放电电压和高的能量密度。
锂二次电池使用能够嵌入及脱嵌锂离子的物质作为负极及正极，且通过在上述正极和负极之间填充电解液来制造。并且，锂二次电池借助锂离子向上述正极及负极嵌入或从上述正极及负极脱嵌时的氧化、还原反应来生成电能。
根据电解液的种类，锂二次电池可分为使用液体电解液的锂二次电池和使用聚合物固体电解液的锂离子聚合物电池。并且，根据聚合物固体电解液的种类，锂离子聚合物电池可分为完全未含有电解液的完全固体型锂离子聚合物电池和使用含有电解液的凝胶型聚合物电解液的锂离子聚合物电池。
在使用上述液体电解液的锂离子电池的情况下，通常对圆筒或方形的金属罐容器实施焊接密封来使用。在方形锂二次电池的情况下，有利于从外部冲击中保护电极组件，且注液工序便捷，相反，但由于形态被固定，因而在减少体积方面存在困难。因此，在将其作为电源的电器产品的情况下，具有设计上受限的缺点。并且，由于在安全性方面放出气体或液体的效果(vent)并不顺畅，导致内部热及气体积累，因而爆炸的危险性变大，且由于无法有效地放出内部的热，因而具有引发过热引起的电池退化的时间变短的缺点。
为了改善这种缺点，最近开发出了将正极(cathode)、负极(anode)及隔膜层叠并卷绕而成的电极组件放入由膜制成的袋形外饰材料，并在进行密封之后，注入电解液来制造的袋形二次电池。
如图1所示，上述袋形外饰材料依次包括：内部层a，具有热粘结性，起到密封材料的作用；金属层b，维持机械强度，并起到水分和氧的阻隔层作用；以及外部层c，起到基材保护层的作用。此时，上述内部层a成为作为聚烯烃类树脂层普遍使用的流延聚丙烯层(CastedPolypropylene；CPP)11及PPa层(请标注英文)13层叠的多层膜结构，上述金属层b由铝层(AL/Aluminum Layer)15构成，上述外部层c成为聚对苯二甲酸乙二醇酯(PET)17及尼龙层层叠的多层膜结构。
在袋形二次电池的情况下，在形态及大小方面没有限制，且便于通过热熔敷来实现组装，并且，当发生异常举动时，能够容易实现排出气体或液体的效果，因而具有安全性高的优点。因此，尤其适合制作薄厚度的电池。
但与方形不同，由于袋形二次电池的外饰材料使用软质的袋作为容器，因而具有物理强度、机械强度弱，密封的可靠性低的缺点。
例如，使用于上述袋形二次电池的电解液包含六氟磷酸锂盐(LiPF6)，而上述六氟磷酸锂盐在充放电过程中分解为Li和PF6，在电解质内提供锂离子，从而利用于增加锂离子的扩散速度。但由于上述六氟磷酸锂盐的亲水性非常好，因而与空气中所包含的相对湿度数％的水分(H2O)发生反应，并与叫作LiOH的氢氧化锂一同生成基于PF6中的一个F原子和H+的反应的氢氟酸(HF)气体。上述氢氟酸气体成为增加袋的厚度甚至引发爆炸的原因。
进而，当成形包装材料时，因内部的压力而使内部树脂层a受损，使得金属层b露出，并与溶解于电解液内的锂离子发生反应23，并在金属层b的表面形成有锂-铝合金25。以这种方式形成的锂-铝合金25与渗透的水分27发生反应，形成氢氟酸气体及微细孔隙，使袋外饰材料更加弱化。其结果，水分能够容易地向被弱化的袋的内部渗透，并增加HF气体，从而在强酸气氛下，使Li-Al合金的溶出更加深化，因而使孔隙的大小逐渐增加29。这最终引发袋外饰材料的腐蚀，从而引起电解液的泄漏(参照图2)。
发明内容
发明要解决的技术问题
在本发明中，为了提高锂二次电池的电性能，提供能够在充放电过程中防止袋外饰材料的腐蚀的新结构的多层袋外饰材料及包含它的袋形二次电池。
解决技术问题的手段
具体地，本发明的一实例提供的袋外饰材料，是锂二次电池的袋外饰材料，
上述袋外饰材料由内部树脂层、中间树脂层及外部树脂层层叠而成。
此时，上述袋外饰材料包含丙烯酸酯-聚氨酯类树脂或环氧类树脂作为中间树脂层。
并且，本发明的另一实例提供的袋形二次电池，包括：电极组件；以及上述袋外饰材料，用于收容上述电极组件。
发明的效果
本发明提供由内部树脂层、中间树脂层及外部树脂层构成的袋外饰材料，从而不仅能够防止袋的腐蚀现象，而且还能抑制由此引起的水分的渗透，能够制造稳定性优良的袋形二次电池。
附图说明
图1为现有的由内部层/金属层/外部层的多层结构构成的袋外饰材料的剖视图。
图2为表示现有的袋外饰材料的腐蚀现象的反应图。
图3为本发明一实施例的由内部树脂层/中间树脂层/外部树脂层的多层结构构成的袋外饰材料的剖视图。
具体实施方式
以下，为了帮助对本发明的理解，对本发明进行更加详细的说明。此时，本说明书及发明请求保护范围所使用的术语或单词不应仅限于通常的或词典上的意义来解释，而是应立足于发明人员为了以最佳方法说明自己的发明而能够适当地定义术语的概念的原则，应以符合本发明的技术思想的意义和概念来解释。
本发明提供一种电池的袋外饰材料，上述袋外饰材料由内部树脂层、中间树脂层及外部树脂层层叠而成。
并且，本发明提供袋形二次电池，其包括：电极组件；以及用于收容该电极组件的上述袋外饰材料。
以下，参照附图对本发明进行更加详细的说明如下。
如图3所示，本发明一实施例的电池的袋外饰材料，包括：内部层A，具有热粘结性，起到密封材料的作用；中间树脂层，维持机械强度，起到防止水分的渗透及电荷的移动而防止副反应的绝缘体层B作用；以及外部层C，起到基材及保护层的作用。
此时，优选地，上述树脂层由一层以上的树脂复合层构成。
具体地，在本发明的袋外饰材料中，上述内部树脂层可包括选自由流延聚丙烯(CPP)、聚丙烯-丁烯-乙烯三元共聚物、聚丙烯、聚乙烯、乙烯丙烯共聚物、聚乙烯和丙烯酸的共聚物及聚丙烯和丙烯酸的共聚物组成的组中的一种的单层或两种以上的复合层。
此时，上述内部树脂层的厚度可以为10μm至100μm。
并且，在本发明的袋外饰材料中，上述中间树脂层可包含丙烯酸酯-聚氨酯类树脂或环氧类树脂。
具体地，上述丙烯酸酯-聚氨酯类树脂还可以包含丙烯腈类树脂。
此时，上述中间树脂层的厚度可以为60μm至100μm。
在本发明的袋外饰材料中，能够通过使树脂熔融或溶解于溶剂来实现膜化之后涂敷或层压于上述内部树脂层的方式形成上述中间树脂层。
此时，上述溶剂只要是能够溶解树脂的溶剂，就不受特殊限制。
并且，在本发明的袋外饰材料中，上述外部树脂层可包括选自聚乙烯、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)及线性低密度聚乙烯(LLDPE)中的一种的单层或两种以上的复合层。
此时，上述外部树脂层的厚度可以为10μm至100μm。
并且，本发明提供袋形二次电池，其包括：电极组件；以及本发明的袋外饰材料，用于收容上述电极组件。
此时，由包含负极活性物质的负极(anode)和包含正极活性物质的正极(cathode)，将隔膜介于中间，并以绝缘方式卷绕，由此构成上述组件。
具体地，例如，正极以在正极集电体上涂敷正极活性物质、导电剂及粘合剂的混合物之后，进行干燥的方式制造，并且，根据需要，还可以在上述混合物添加填充剂。
本发明的正极活性物质，能够使用锂钴氧化物(LiCoO2)、锂镍氧化物(LiNiO2)等层状氧化物或被一种或其以上的过渡金属取代的化合物；化学式Li1+xMn2-xO4(其中，x为0至0.33)、LiMnO3、LiMn2O3、LiMnO2等锂锰氧化物(LiMnO2)；锂铜氧化物(Li2CuO2)；LiV3O8、LiFe3O4、V2O5、Cu2V2O7等钒氧化物；以化学式LiNi1-xMxO2(其中，M＝Co、Mn、Al、Cu、Fe、Mg、B或Ga，x为0.01至0.3)表示的锂镍氧化物(lithiated nickel oxide)；以化学式LiMn2-xMxO2(其中，M＝Co、Ni、Fe、Cr、Zn或Ta，x为0.01至0.1)或Li2Mn3MO8(其中，M为Fe、Co、Ni、Cu或Zn)表示的锂锰复合氧化物；化学式的锂的一部分被碱土金属离子取代的LiMn2O4；二硫化合物；Fe2(MoO4)3或混合使用基于它们的组合来形成的复合氧化物等锂吸附物质(lithiumintercalation material)作为主要成分的化合物。
上述正极集电体的厚度通常为3μm至500μm。这种正极集电体只要是不会在相应电池引发化学变化，且具有高的导电性的，就不受特殊限制，例如，可以使用不锈钢、铝、镍、钛、煅烧碳或利用碳、镍、钛、银等对铝或不锈钢的表面进行表面处理的物质等。集电体可在其表面形成有细微的凹凸来提高正极活性物质的粘结力，并能使用为膜、薄片、箔、网、多孔质体、发泡体及无纺布体等多种形态。
通常，以包含正极活性物质的混合物的总重量为基准，添加1重量百分比至50重量百分比的上述导电剂。这种导电剂只要是不会在相应电池引发化学变化，且具有导电性的，就不受特殊限制，例如，可以使用天然石墨或人造石墨等石墨；炭黑、乙炔黑、科琴黑、槽法炭黑、炉黑、灯黑及热炭黑等炭黑；碳纤维或金属纤维等导电性纤维；氟化碳、铝、镍粉末等金属粉末；氧化锌、钛酸钾等导电性晶须；氧化钛等导电性氧化物；聚苯撑衍生物等导电性材料等。
上述粘合剂是有助于活性物质和导电剂等的结合以及对集电体的结合的成分，以包含正极活性物质的混合物的总重量为基准，通常添加1至50重量百分比的上述粘合剂。作为这种粘合剂的例，可以举出聚偏氟乙烯、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-丙烯二烯三元共聚物(EPDM)、磺化EPDM、丁苯橡胶、氟橡胶、多种共聚物等。
上述填充剂作为用于抑制正极的膨胀的成分，是选择性使用的，只要不会在相应电池引发化学变化，且为纤维状材料，就不受特殊限制，例如，使用聚乙烯、聚丙烯等烯烃类聚合物；玻璃纤维、碳纤维等纤维状物质。
另外，负极可以通过在负极集电体上涂敷负极材料，并进行干燥来制作，根据需要，还可以包括如上所述的成分。
上述负极集电体的厚度通常为3μm至500μm。这种负极集电体只要是不会在相应电池引发化学变化，且具有导电性的，就不受特殊限制，例如，可以使用铜、不锈钢、铝、镍、钛、煅烧碳、利用碳、镍、钛、银等对铜或不锈钢的表面进行表面处理的物质及铝-镉合金等。并且，与正极集电体一样，可以在表面形成微细的凹凸来强化负极活性物质的结合力，并能使用为膜、薄片、箔、网、多孔质体、发泡体及无纺布体等多种形态。
上述负极材料包含非晶质碳或晶质碳，具体地，可使用难石墨化碳、石墨类碳等碳；LixFe2O3(0≤x≤1)、LixWO2(0≤x≤1)、SnxMe1-xMe'yOz(Me为Mn、Fe、Pb、Ge；Me'为Al、B、P、Si、周期表的1族、2族、3族元素、卤素；0＜x≤1；1≤y≤3；1≤z≤8)等金属复合氧化物；锂金属；锂合金；硅类合金；锡类合金；SnO、SnO2、PbO、PbO2、Pb2O3、Pb3O4、Sb2O3、Sb2O4、Sb2O5、GeO、GeO2、Bi2O3、Bi2O4或Bi2O5等氧化物；聚乙炔等导电性聚合物；Li-Co-Ni类材料等。
作为在上述正极和负极之间使上述电极之间绝缘的隔膜，可以使用通常公知的聚烯烃类隔膜或在烯烃类基材形成有有机无机复合层的复合隔膜等，但不受特殊限制。
将以如上所述的结构构成的电极集电体收纳于袋外饰材料之后，注入电解液，由此制造电池。
本发明的电解液是含锂盐非水系电解质，其由非水电解质和锂组成。作为非水电解质，使用非水电解液、固体电解质及无机固体电解质等。
作为上述非水电解液，例如，可以使用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、二甲基亚砜、1,3-二氧戊环、甲酰胺、二甲基甲酰胺、二氧环戊烷、乙腈、硝基甲烷、甲酸甲酯、乙酸甲酯、磷酸三酯、三甲氧基甲烷、二氧环戊烷衍生物、环丁砜、甲基环丁砜、1,3-二甲基-2-咪唑啉酮、碳酸丙烯酯衍生物、四氢呋喃衍生物、醚、丙酸甲酯、丙酸乙酯等非质子性有机溶剂。
作为上述有机固体电解质，例如，可以使用聚乙烯衍生物、聚环氧乙烷衍生物、聚环氧丙烷衍生物、磷酸酯聚合物、多聚聚赖氨酸(agitation lysine)、聚酯硫醚、聚乙烯醇、聚偏氟乙烯、包含离子性解离基的聚合物等。
作为上述无机固体电解质，例如，可以使用Li3N、LiI、Li5NI2、Li3N-LiI-LiOH、LiSiO4、LiSiO4-LiI-LiOH、Li2SiS3、Li4SiO4、Li4SiO4-LiI-LiOH、Li3PO4-Li2S-SiS2等Li的氮化物、卤化物及硫酸盐等。
上述锂盐作为易于溶解在上述非水系电解质的物质，例如，可以使用LiCl、LiBr、LiI、LiClO4、LiBF4、LiB10Cl10、LiPF6、LiCF3SO3、LiCF3CO2、LiAsF6、LiSbF6、LiAlCl4、CH3SO3Li、CF3SO3Li、(CF3SO2)2NLi、氯硼烷锂、低级脂肪族羧酸锂、4-苯基硼酸锂、酰亚胺等。
并且，在非水系电解质中，还可以添加例如吡啶、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、硫磺、醌亚胺染料、N-取代恶唑烷酮、N,N-取代咪唑啉、乙二醇二烷基醚、铵盐、吡咯、2-甲氧基乙醇、三氯化铝等，以改善充放电特性、难燃性等。根据情况，可以为了赋予不燃性而还包含四氯化碳、三氟化乙烯等含卤素的溶剂，可以为了提高高温保存特性而还包含二氧化碳气体。
另一方面，优选地，如上所述的袋形二次电池为锂二次电池，但并不局限于此。
本发明的袋形二次电池，可作为大中型装置的电源的电池模块的单元电池使用。
附图标记的说明
11、31：CPP层
13、33：PPa层
15：铝箔
17：PET层
19、39：尼龙层
23：电解液内所含的锂盐
25：锂-铝合金
27：水分渗透
29：增加的孔隙大小
a、A：内部树脂层
b：金属层
B：绝缘体层
c、C：外部树脂层
Claims (12)
1.一种袋外饰材料，是二次电池的袋外饰材料，其特征在于，所述外饰材料由内部树脂层、中间树脂层及外部树脂层层叠而成。
2.根据权利要求1所述的袋外饰材料，其特征在于，所述内部树脂层及外部树脂层分别是由一层以上构成的树脂复合层。
3.根据权利要求1所述的袋外饰材料，其特征在于，所述内部树脂层包括选自由流延聚丙烯、聚丙烯-丁烯-乙烯三元共聚物、聚丙烯、聚乙烯、乙烯丙烯共聚物、聚乙烯和丙烯酸的共聚物及聚丙烯和丙烯酸的共聚物组成的组中的一种的单层或两种以上的复合层。
4.根据权利要求1所述的袋外饰材料，其特征在于，所述内部树脂层的厚度为10μm至100μm。
5.根据权利要求1所述的袋外饰材料，其特征在于，所述中间树脂层包含丙烯酸酯-聚氨酯类树脂或环氧类树脂。
6.根据权利要求5所述的袋外饰材料，其特征在于，所述丙烯酸酯-聚氨酯类树脂还包含丙烯腈类树脂。
7.根据权利要求1所述的袋外饰材料，其特征在于，所述中间树脂层的厚度为60μm至100μm。
8.根据权利要求1所述的袋外饰材料，其特征在于，所述中间树脂层是通过使树脂熔融或溶解于溶剂来实现膜化之后涂敷或层压于所述内部树脂层的方式形成的。
9.根据权利要求1所述的袋外饰材料，其特征在于，所述外部树脂层包括选自聚乙烯、聚丙烯、聚对苯二甲酸乙二醇酯、尼龙、低密度聚乙烯、高密度聚乙烯及线性低密度聚乙烯中的一种的单层或两种以上的复合层。
10.根据权利要求1所述的袋外饰材料，其特征在于，所述外部树脂层的厚度为10μm至100μm。
11.一种袋形二次电池，其特征在于，包括：
电极组件；以及
如权利要求1所述的袋外饰材料，用于收容上述电极组件。
12.根据权利要求11所述的袋形二次电池，其特征在于，所述袋形二次电池作为大中型装置的电源的电池模块的单元电池使用。
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