CN109964358A - 非水电解质二次电池 - Google Patents
非水电解质二次电池 Download PDFInfo
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- CN109964358A CN109964358A CN201780071371.0A CN201780071371A CN109964358A CN 109964358 A CN109964358 A CN 109964358A CN 201780071371 A CN201780071371 A CN 201780071371A CN 109964358 A CN109964358 A CN 109964358A
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- 239000007832 Na2SO4 Substances 0.000 claims description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
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- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims 1
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- 229910002804 graphite Inorganic materials 0.000 description 2
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- CEDDGDWODCGBFQ-UHFFFAOYSA-N carbamimidoylazanium;hydron;phosphate Chemical compound NC(N)=N.OP(O)(O)=O CEDDGDWODCGBFQ-UHFFFAOYSA-N 0.000 description 1
- LNEUSAPFBRDCPM-UHFFFAOYSA-N carbamimidoylazanium;sulfamate Chemical compound NC(N)=N.NS(O)(=O)=O LNEUSAPFBRDCPM-UHFFFAOYSA-N 0.000 description 1
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- FYIBGDKNYYMMAG-UHFFFAOYSA-N ethane-1,2-diol;terephthalic acid Chemical compound OCCO.OC(=O)C1=CC=C(C(O)=O)C=C1 FYIBGDKNYYMMAG-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/116—Primary casings; Jackets or wrappings characterised by the material
- H01M50/124—Primary casings; Jackets or wrappings characterised by the material having a layered structure
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- H—ELECTRICITY
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
- H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
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- H01M50/102—Primary casings; Jackets or wrappings characterised by their shape or physical structure
- H01M50/103—Primary casings; Jackets or wrappings characterised by their shape or physical structure prismatic or rectangular
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- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/116—Primary casings; Jackets or wrappings characterised by the material
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- H01M50/584—Means for preventing undesired use or discharge for preventing incorrect connections inside or outside the batteries
- H01M50/59—Means for preventing undesired use or discharge for preventing incorrect connections inside or outside the batteries characterised by the protection means
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
非水电解质二次电池具备使正负电极夹着分隔件重叠而成的电极体、配置在上述电极体的外周上的覆盖体、和非水电解质。覆盖体是具有伸展性树脂层和包含吸热材料的吸热层的多层结构。
Description
技术领域
本公开涉及非水电解质二次电池技术。
背景技术
作为非水电解质二次电池,已知将包含正极、分隔件和负极的电极体收容在由层压片形成的外壳体内的层压型电池、收容在方形壳体内的方形电池等。
另外,作为确认电池对于内部短路的耐受性的安全性评价试验,有钉刺试验。钉刺试验例如为如下试验:使钉子沿着电极体的厚度方向穿刺而模拟产生内部短路,调查发热程度来确认电池的安全性。抑制这样的钉刺时的电池发热对于确保电池的安全性而言很重要。
例如,专利文献1~3公开了在正极、负极或分隔件上配置具有伸展性的覆盖层来抑制钉刺时的电池发热的技术。
现有技术文献
专利文献
专利文献1:日本特开2000-21386号公报
专利文献2:日本特开2004-363048号公报
专利文献3:日本特开2012-190587号公报
发明内容
但是,随着非水电解质二次电池的高能量密度化,钉刺时的电池发热量变得非常大,因此存在覆盖层熔融、不能充分抑制钉刺时的电池发热的情况。
因此,本公开的目的在于,提供能够抑制钉刺时的电池发热的非水电解质二次电池。
作为本公开的一方式的非水电解质二次电池具备:使正负电极夹着分隔件重叠而成的电极体、配置在上述电极体的外周上的覆盖体、和非水电解质。上述覆盖体为具有伸展性树脂层和包含吸热材料的吸热层的多层结构。
根据本公开的非水电解质二次电池,能够抑制钉刺时的电池发热。
附图说明
图1是本实施方式的非水电解质二次电池的立体图。
图2是图1的II-II线截面图。
图3是本实施方式中使用的覆盖体的局部截面图。
图4是示出发生钉刺时的电极体的状态的局部放大截面图。
图5A是另一实施方式的覆盖体的局部截面图。
图5B是又一实施方式的覆盖体的局部截面图。
图5C是再一实施方式的覆盖体的局部截面图。
图6是层叠电极体及覆盖体的截面图。
具体实施方式
以下边参照附图边对实施方式的一例进行详细说明。实施方式的说明中所参照的附图是示意性记载,图中描绘的构成要素的尺寸比率等有时与实物不同。关于本说明书中的“大致**”的记载,如果以大致垂直为例来说明,则意图在于:当然包括完全垂直、还包括可认为实质上垂直的情况。
图1是本实施方式的非水电解质二次电池的立体图,图2是图1的II-II线截面图。本实施方式中使用的非水电解质二次电池是俯视形状为大致矩形、厚度比该大致矩形的长宽尺寸薄的板状的电池单元。
如图1及2所示,非水电解质二次电池10是在作为外壳体的壳体12内封入了电极体15、配置在电极体15的外周上的覆盖体18、及非水电解质的方形电池。壳体12通过将大致箱形状的壳主体13的上部开口部用作为封口体的盖板14堵住而形成。壳主体13和盖板14通过例如熔接而接合。
电极体15例如是在正极集电体的规定区域形成有正极活性物质层的正极、与在负极集电体的规定区域形成有负极活性物质层的负极夹着分隔件交替地层叠多层而成的层叠型电极体,也可以是上述正极与上述负极夹着分隔件卷绕而成的卷绕型电极体等。
正极集电体可列举铝等在正极的电位范围内稳定的金属的箔、在表层配置有该金属的膜等。正极活性物质层优选除了正极活性物质以外还包含导电材料及粘结材料、且设置在集电体的两面。正极活性物质例如使用含锂的复合氧化物。作为优选的复合氧化物的一例,可列举Ni-Co-Mn系、Ni-Co-Al系的含锂的复合氧化物。
负极集电体可列举铜等在负极的电位范围内稳定的金属的箔、在表层配置有该金属的膜等。负极活性物质层优选除了负极活性物质以外还包含粘结材料、且设置在集电体的两面。作为负极活性物质,只要是能够吸藏释放锂离子的材料即可,通常使用石墨。
分隔件使用具有离子透过性及绝缘性的多孔片等。作为多孔片的具体例子,可列举微多孔薄膜、织布、无纺布等。作为分隔件的材质,优选聚乙烯、聚丙烯等烯烃系树脂、纤维素等。
非水电解质包含非水溶剂和溶解在非水溶剂中的电解质盐。非水电解质不限于液体电解质,也可以是使用凝胶状聚合物等的固体电解质。作为非水溶剂,可以使用例如:碳酸亚乙酯、碳酸亚丙酯、碳酸亚丁酯等环状碳酸酯;碳酸二甲酯、碳酸甲乙酯、碳酸二乙酯等链状碳酸酯;环状碳酸酯与链状碳酸酯的混合溶剂等。作为电解质盐,可列举例如LiPF6、LiBF4、LICF3SO3等。
覆盖体18例如为带状的膜,通过将带状的膜卷绕在电极体15的外周而配置在电极体15的外周上。或者覆盖体18为袋状的膜,通过在其中收容电极体15而配置在电极体15的外周上。另外,在覆盖体18与电极体15之间可以夹设粘接剂。覆盖体18的具体构成将在后文说明。
非水电解质二次电池10具有:安装于盖板14的负极端子16及正极端子17。负极端子16与从构成电极体15的负极集电体引出的负极极耳(未图示)电连接,以便集电。正极端子17与从构成电极体15的正极集电体引出的正极极耳(未图示)电连接,以便集电。
壳主体13例如使用由铁、不锈钢等铁系合金、铝、铝系合金等金属材料形成,且形成为有底箱状的壳体。盖板14例如由与壳主体13同样的材料构成。
图3是本实施方式中使用的覆盖体18的局部截面图。覆盖体18由伸展性树脂层26和包含吸热材料的吸热层28构成。
伸展性树脂层26是在承受应力时产生伸长的树脂片,例如优选沿着长度方向拉伸时的最大伸长率(断裂伸长率)为500%以上。伸展性树脂层26例如由聚氨酯系弹性体、聚酯系弹性体、聚苯乙烯系弹性体、聚烯烃系弹性体、聚酰胺系弹性体等构成。这些中优选伸展性高的聚氨酯系弹性体。聚氨酯系弹性体可列举例如聚氨酯、聚氨酯·聚脲弹性体等,从伸展性等的角度出发优选聚氨酯。树脂层26的厚度是任意的,优选例如20μm~200μm的范围。
包含吸热材料的吸热层28例如通过将在分散介质中分散有吸热材料的颗粒的浆料涂布在树脂层26上而形成。吸热材料只要是能够吸收或消耗热量的物质即可,其成分、含量等没有特别限制。吸热材料吸收或消耗热量的温度优选为非水电解质二次电池的正常工作温度以上的温度。具体而言,非水电解质二次电池的正常工作温度为最高90℃左右,因此吸热材料吸收或消耗热量的温度更优选为例如100℃以上。吸热层28的厚度是任意的,优选例如2μm~20μm的范围。
作为吸热材料的例子,可列举含锑化合物、金属氢氧化物、钠盐水合物、胍基系化合物、含硼化合物、酒石酸锌等。作为含锑化合物,可列举例如三氧化锑、四氧化锑、五氧化锑等。作为金属氢氧化物,可列举例如氢氧化铝、氢氧化镁等。作为钠盐水合物,可列举例如硫酸钠十水合物、碳酸钠十水合物等。作为胍基系化合物,可列举例如:硝酸、胍、氨基磺酸胍、磷酸胍、磷酸胍基脲等。作为含硼化合物,可列举例如H3BO3、HBO2等。作为酒石酸锌化合物,可列举例如Zn2SnO4、ZnSnO3、ZnSn(OH)6等。这些中,从非水电解质二次电池10中产生的热量的吸收量等角度出发,优选氢氧化铝、硫酸钠十水合物或它们的混合物。
氢氧化铝在200℃以上显示以下的吸热反应。
Al(OH)3→0.5Al2O3+1.5H2O
硫酸钠十水合物在100℃以上显示以下的吸热反应。
Na2SO4·10H2O→Na2SO4+10H2O
分散介质可列举例如高分子粘结剂等。高分子粘结剂可列举例如聚偏氟乙烯、聚甲基丙烯酸甲酯、聚丙烯腈、聚乙二醇等。
图4是显示发生钉刺时的电极体的状态的局部放大截面图。通常,当非水电解质二次电池被钉子穿刺时,例如钉子5穿透正极1、分隔件3而到达负极2。并且正极集电体1a及正极活性物质层1b与钉子5直接接触,且负极集电体2a及负极活性物质层2b也与钉子5直接接触。由此,在正极集电体1a与负极集电体2a之间介由钉子5而产生内部短路、流过短路电流,因此非水电解质二次电池发热而达到正常工作温度以上。但是,在本实施方式中,即使在钉子5刺穿电极体时,由于配置在电极体的外周的覆盖体18沿着钉子5伸长,因此也在钉子5与正极集电体1a、负极集电体2a之间夹设覆盖体18的树脂层。由此,经由钉子5的正极集电体1a与负极集电体2a之间的电阻增大,抑制了流过大的短路电流的情况,因此电池的发热量得到抑制。进而,覆盖体18的吸热层吸收、消耗了由于电池的内部短路而产生的热量,因此电池的发热被更有效地抑制。
进而,认为通过使用本实施方式的覆盖体而具有以下的次要效果。(1)在使用多个非水电解质二次电池组成模块时,通过非水电解质二次电池的发热抑制效果而能够抑制热量对相邻的非水电解质二次电池的影响。(2)通过覆盖体将电极体固定,能够防止由施加于电池的振动、冲击导致的电极体在壳体内移动,另一方面在因电极体随着充放电、实际使用(电池的充放电循环、保存)而膨胀所产生的力(以下称为反作用力)增加时,能够利用覆盖体来吸收该反作用力。(3)由于仅在电极体的外周设置覆盖体,因此与在各电极、各分隔件设置覆盖体时相比能够减小非水电解质二次电池的厚度,电池的能量密度的降低小。
在图3所示的覆盖体18中,与电极体接触的面可以是树脂层26也可以是吸热层28。即,覆盖体18从电极体的外周上起可以依次配置树脂层26/吸热层28,也可以依次配置吸热层28/树脂层26。其中,从通过使发热的电极体与吸热层28接触而能够使电极体的发热高效地传热并吸收至吸热层28的吸热材料,或者可以有效提高夹着钉子5的正极1、负极2之间的电阻等的角度出发,理想的是从电极体的外周上起依次配置吸热层28/树脂层26(理想的是将覆盖体18的最外层设为树脂层26)。
图3所示的覆盖体18为树脂层26及吸热层28的2层构成,但在本实施方式中除了这些层以外可以进一步包含辅助的层。以下对覆盖体18的其它实施方式进行说明。
图5A~图5C是另一实施方式的覆盖体的局部截面图。在图5A~图5C所示的覆盖体中,与图3所示的覆盖体相同的构成标注有相同的符号。图5A所示的覆盖体18依次层叠吸热层28/树脂层26/基材层30。另外,图5B所示的覆盖体18依次层叠树脂层26/吸热层28/树脂层26。另外,图5C所示的覆盖体18依次层叠基材层30/树脂层26/吸热层28/树脂层26/基材层30。
构成图5A、图5C的覆盖体18的基材层30例如是以有机材料为主体的层,具体而言,可列举PE(聚乙烯)、PPS(聚苯硫醚)、PEEK(聚醚醚酮)、PI(聚酰亚胺)、PP(聚丙烯)、PET(聚对苯二甲酸乙二醇酯)PBT(聚对苯二甲酸丁二醇酯)等。通过设置基材层30,能够提高覆盖体18的强度。基材层30的厚度是任意的,优选例如20μm~100μm的范围。
通过如图5B、图5C的覆盖体18那样设为用树脂层26挟持吸热层28的两侧的结构,从而能够抑制由吸热材料与电解液接触所导致的副反应。
另外,具备基材层30的覆盖体18中,优选将基材层30设为覆盖体18的最外层。即,在图5A所示的覆盖体18中,优选从电极体的外周上起依次配置吸热层28/树脂层26/基材层30。由此,能够抑制由树脂层26与电解液接触所导致的树脂层26劣化、吸热材料与电解液接触所导致的副反应。
在非水电解质二次电池中具备层叠多个电极体15而成的层叠电极体32时,优选如图6所示那样在层叠电极体32的外周上配置覆盖体18、且在构成层叠电极体32的电极体15间配置覆盖体18。
需要说明的是,作为非水电解质二次电池的形态,不限于方形,可以例示层压型、圆筒型、方型、硬币型、纽扣型等。
实施例
以下通过实施例进一步说明本实施方式,但本实施方式不受这些实施例限定。
<实验例1>
(电池单元的制作)
将包含作为正极活性物质的LiNi0.35Mn0.35Co0.3O2的正极复合材料浆料涂布在铝箔(厚:15μm)的两面后,进行干燥、压延,制作正极极耳从正极复合材料涂布部分突出的形状的正极。然后,将包含作为负极活性物质的石墨的负极复合材料浆料涂布在铜箔(厚:10μm)的两面后,进行干燥、压延,制作负极极耳从负极复合材料涂布部分突出的形状的负极。然后,将上述正极和上述负极夹着分隔件交替层叠,由此制作层叠型的电极体。
然后,将依次层叠基材层(厚70μm)/伸展性树脂层(厚100μm)/吸热层(厚10μm)/伸展性树脂层(厚100μm)/基材层(厚70μm)而成的膜作为覆盖体,卷绕在上述电极体的外周上。伸展性树脂层使用聚氨酯膜(伸长率300%以上)。另外,吸热层通过将在聚偏氟乙烯中分散有作为吸热材料的氢氧化铝的浆料涂布在聚氨酯膜上而形成。基材层通过使用聚乙烯,热封于与吸热层位于相反侧的树脂层上而形成。
将向碳酸亚乙酯(EC)、碳酸亚丙酯(PC)、碳酸二乙酯(DEC)按照体积比25:5:75的比例混合而成的混合溶剂中以1M(摩尔/升)的比例溶解LiPF6而成的液体作为电解液使用。
将制作的电极体的正极极耳安装于与盖体上所安装的正极端子连接的正极端子板,将负极极耳安装于与盖体上所安装的负极端子连接的负极端子板。然后,从壳主体的开口部插入电极体,并且用盖体封堵壳主体的开口部,将壳体开口周缘与盖体周缘进行激光熔接。然后,从盖体上所设置的注液口注入上述电解液后,将注液口密封,由此制作方型的电池单元。
<实施例2>
将吸热材料由氢氧化铝变更为硫酸钠十水合物,除此以外与实施例1同样地制作电池单元。
<比较例1>
不使用覆盖体,除此以外与实施例1同样制作电池单元。
<比较例2>
作为覆盖体,使用依次层叠基材层(厚度70μm)/伸展性树脂层(厚100μm)而成的膜,除此以外与实施例1同样地制作电池单元。
(钉刺试验)
以充电电流80A将各实施例及比较例的电池单元在恒定电流下充电到4.2V。然后,以电压4.2V在恒定电压下充电至充电电流为4A。用一对SUS板从两侧挟持充电后的电池单元,而将电池单元固定。另外,在电池单元的表面中央部附近设置热电偶。然后使用钉刺试验装置,将钉刺位置设定为电池单元的中央,使的钉子以25mm/秒的速度贯穿。利用设置在电池单元的表面中央部附近的热电偶测定钉刺后的电池单元的最高温度。
对于钉刺后的电池单元的最高温度,实施例1的电池单元中为320℃,实施例2的电池单元中为313℃,比较例1的电池单元中为391℃,比较例2的电池单元中为342℃。由该结果可知,通过将具备伸展性树脂层及吸热层的覆盖体配置在电极体的外周,由此能够抑制钉刺后的电池发热。
附图标记说明
1 正极
1a 正极集电体
1b 正极活性物质层
2 负极
2a 负极集电体
2b 负极活性物质层
3 分隔件
5 钉子
10 非水电解质二次电池
12 壳体
13 壳主体
14 盖板
15 电极体
16 负极端子
17 正极端子
18 覆盖体
26 树脂层
28 吸热层
30 基材层
32 层叠电极体
Claims (5)
1.一种非水电解质二次电池,其具备使正负电极夹着分隔件重叠而成的电极体、配置在所述电极体的外周上的覆盖体、和非水电解质,
所述覆盖体为具有伸展性树脂层和包含吸热材料的吸热层的多层结构。
2.根据权利要求1所述的非水电解质二次电池,其中,所述覆盖体是依次层叠伸展性树脂层/包含吸热材料的吸热层/伸展性树脂层而成的。
3.根据权利要求1或2所述的非水电解质二次电池,其中,所述树脂层为聚氨酯。
4.根据权利要求1~3中任一项所述的非水电解质二次电池,其中,所述吸热材料为氢氧化铝(Al(OH)3)、硫酸钠十水合物(Na2SO4·10H2O)或它们的混合物。
5.根据权利要求1~4中任一项所述的非水电解质二次电池,其具备层叠多个所述电极体而成的层叠电极体,
所述覆盖体配置在所述层叠电极体的外周上、及构成所述层叠电极体的电极体间。
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US11258124B2 (en) | 2022-02-22 |
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