CN107331801A - 锂二次电池及其制备方法 - Google Patents
锂二次电池及其制备方法 Download PDFInfo
- Publication number
- CN107331801A CN107331801A CN201710201367.3A CN201710201367A CN107331801A CN 107331801 A CN107331801 A CN 107331801A CN 201710201367 A CN201710201367 A CN 201710201367A CN 107331801 A CN107331801 A CN 107331801A
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- battery
- lithium secondary
- secondary battery
- battery container
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- 239000004411 aluminium Substances 0.000 claims description 23
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- 159000000002 lithium salts Chemical class 0.000 description 3
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- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
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- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
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- 239000011159 matrix material Substances 0.000 description 2
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
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- 239000004332 silver Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
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- 238000003466 welding Methods 0.000 description 2
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical class CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
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- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229910000925 Cd alloy Inorganic materials 0.000 description 1
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- 101000598921 Homo sapiens Orexin Proteins 0.000 description 1
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- CKFRRHLHAJZIIN-UHFFFAOYSA-N cobalt lithium Chemical compound [Li].[Co] CKFRRHLHAJZIIN-UHFFFAOYSA-N 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical class [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
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- 150000001993 dienes Chemical class 0.000 description 1
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- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
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- 229910052732 germanium Inorganic materials 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
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- 229910052745 lead Inorganic materials 0.000 description 1
- YADSGOSSYOOKMP-UHFFFAOYSA-N lead dioxide Inorganic materials O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 description 1
- XMFOQHDPRMAJNU-UHFFFAOYSA-N lead(II,IV) oxide Inorganic materials O1[Pb]O[Pb]11O[Pb]O1 XMFOQHDPRMAJNU-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- 229910001547 lithium hexafluoroantimonate(V) Inorganic materials 0.000 description 1
- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 0.000 description 1
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Inorganic materials [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 1
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 229910001537 lithium tetrachloroaluminate Inorganic materials 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- 229910021437 lithium-transition metal oxide Inorganic materials 0.000 description 1
- HSFDLPWPRRSVSM-UHFFFAOYSA-M lithium;2,2,2-trifluoroacetate Chemical compound [Li+].[O-]C(=O)C(F)(F)F HSFDLPWPRRSVSM-UHFFFAOYSA-M 0.000 description 1
- VROAXDSNYPAOBJ-UHFFFAOYSA-N lithium;oxido(oxo)nickel Chemical compound [Li+].[O-][Ni]=O VROAXDSNYPAOBJ-UHFFFAOYSA-N 0.000 description 1
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
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- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
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- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
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- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- RIUWBIIVUYSTCN-UHFFFAOYSA-N trilithium borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-] RIUWBIIVUYSTCN-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
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Classifications
-
- 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
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/183—Sealing members
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
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Abstract
本发明提供一种锂二次电池及其制备方法。所述锂离子二次电池包括:电极组件;容纳电极组件的电池壳体;位于电池壳体的外侧上包含工程塑料的表层;以及连接到电极组件并引出至电池壳体之外的引线端子。
Description
相关申请的交叉引用
本申请要求于2016年3月30日提交的韩国专利申请No.10-2016-0038054的的优先权和权益,该申请的公开内容通过引用而全文结合在此。
技术领域
本发明涉及一种锂二次电池及其制备方法。
背景技术
近来,可充电的二次电池已广泛用作无线移动装置的能源。二次电池作为电动车(EVs)、混合动力车(HEVs)等的动力源也受到了关注,这些电动车被认为是用于解决由使用化石燃料的常规汽油车或柴油车造成的空气污染的解决方案。
通常,就电池的形状而言,对于可应用到诸如移动电话等产品的薄棱柱形和袋型二次电池存在大量的需求。就电极的材料而言,对于诸如锂离子电池、锂离子聚合物电池等的锂二次电池存在大量的需求,所述锂二次电池具有例如高能量密度、放电电压、输出稳定等的优点。
近来,因为袋型电池的生产成本低、重量小或易于变形,这种电池引起极大的关注,并且其应用已逐渐增加,所述袋型电池具有电极组件安装在由含铝层压片制成的袋型电池壳体中的结构。
然而,这种袋型电池具有由包含在袋型电池外壳中的铝引起短路的问题。另外,即使是将壳体在引线端子和袋型电池壳体之间的界面处进行热封,袋型电池壳体内的电解质也经常泄漏。
发明内容
本发明致力于提供一种具有优异密封性的锂二次电池。
本发明还致力于提供一种具有优异绝缘性的锂二次电池。
本发明还致力于提供一种具有降低的生产成本和简单的制备方法的锂二次电池。
为了解决上述问题,本发明提供了一种锂二次电池,包括:电极组件;电池壳体,构造为容纳电极组件;包含工程塑料的表层,位于电池壳体的外侧上;以及,引线端子,连接到电极组件并引出至电池壳体之外。
另外,本发明提供了一种锂二次电池的制备方法,包括:在容纳电极组件的电池壳体的外侧上形成包含工程塑料的表层,以便将与电极组件连接的引线端子引出至电池壳体之外。
附图说明
通过下面结合附图的详细描述,本发明的上述和其它目的、特征和优点对于本领域技术人员来说变得更加显而易见,其中:
图1是根据本发明一个实施方式的锂二次电池的平面图;
图2是根据本发明一个实施方式的锂二次电池的剖面图;
图3是根据本发明另一实施方式的锂二次电池的剖面图。
具体实施方式
在下文中,将更详细地描述本发明以帮助理解本发明。
本说明书和权利要求中使用的术语和词语不应解释为限于常规含义或字面含义,而应按照发明人适当地定义术语的概念以便以最佳方式描述本发明的原则,解释为与本发明的技术范围一致的含义和概念。
图1是根据本发明一个实施方式的锂二次电池的平面图,图2是根据本发明一个实施方式的锂二次电池的剖面图。
参照图1和图2,根据本发明一个实施方式,在锂二次电池100中所包括的电极组件110包括:正极(未示出)、负极(未示出)、以及位于正极和负极之间的隔板(未示出)。
正极包括正极集电器,以及在该正极集电器上的正极活性材料、导电材料和粘合剂的混合物。该混合物可以进一步包括填料。
正极集电器具有高导电率且不会在本发明的锂二次电池内引起化学变化。正极集电器可以具有不平的表面以便增加正极活性材料的粘附强度,并且正极集电器可以具有包括膜、片、箔、网、多孔体、泡沫体、无纺布基体等在内的各种形状。正极集电器的具体例可以为不锈钢、铝、镍、钛、烧结碳、或铝。另外,不锈钢表面可以用碳、镍、钛、或银进行处理。
正极活性材料的具体例可以为层状化合物,例如锂过渡金属氧化物、锂钴氧化物(LiCoO2)、或锂镍氧化物(LiNiO2);被至少一个或两个过渡金属取代的化合物;式Li1+xMn2- xO4(x=0至0.33)表示的锂锰氧化物、LiMnO3、LiMn2O3、或LiMnO2;锂铜氧化物(Li2CuO2);钒氧化物,例如LiV3O8、LiFe3O4、V2O5、或Cu2V2O7;式LiNi1-xMxO2(M=Co、Mn、Al、Cu、Fe、Mg、B或Ga,以及x=0.01至0.3)表示的锂锰复合氧化物;LiNixMn2-xO4表示的具有尖晶石结构的锂锰氧化物;LiMn2O4,其中所述式中部分锂被碱土金属离子替代;二硫化物;Fe2(MoO4)3;或镍钴锰氧化物。
导电材料具有导电性,且不会在本发明的锂二次电池中引起化学变化。导电材料的具体例可以是石墨,例如天然石墨或人工石墨;碳黑,例如乙炔黑、Ketjen黑、槽法炭黑、炉黑、灯黑或热炭黑;导电纤维,例如碳纤维或金属纤维;金属粉,例如氟化碳、铝或镍粉;导电晶须,例如氧化锌或钛酸钾;导电金属氧化物,例如氧化钛;或导电物质,例如聚苯撑的衍生物。
粘合剂是对在正极活性材料和导电材料等之间的粘结、以及粘结至集电器起到帮助的一种组分。粘合剂的具体例可包括聚偏二氟乙烯、聚乙烯醇、羧甲基纤维(CMC)、淀粉、羟苯基纤维素、再生纤维素、聚乙烯吡咯烷酮、四氟乙烯、聚乙烯、聚丙烯、乙丙二烯单体(EPDM)橡胶、氢化腈丁二烯橡胶(HNBR)、磺化的EPDM、丁苯橡胶、氟橡胶、各种共聚物等。
填料是抑制正极膨胀的一种组分,并且填料是一种不会在本发明的锂二次电池中引起化学变化的纤维材料。填料的实例可包括烯烃基聚合物,例如聚乙烯、聚丙烯等;纤维材料,例如玻璃纤维、碳纤维等;以及诸如此类。
负极包括负极集电器和位于负极集电器上的负极活性材料。负极可进一步包括导电材料、粘合剂、填料等。
负极集电器具有导电性,且不会在电池中引起化学变化。负极集电器的具体例可以为铜、不锈钢、铝、铝-镉合金、镍、钛、或烧结碳。铜或不锈钢的表面可以用碳、镍、钛或银进行处理。与正极集电器一样,负极集电器可具有略不平整的表面,以增强负极活性材料的粘结强度,并且负极集电器可以是以包括膜、片、箔、网、多孔体、泡沫体、无纺布基体等在内的各种形式使用。
负极活性材料的具体例可以为碳,例如硬碳或石墨基碳;金属复合氧化物,例如LixFe2O3(0≤x≤1)、LixWO2(0≤x≤1)、或SnxMe1-xMe'yOz(Me=Mn、Fe、Pb、Ge;Me'=Al、B、P、Si、周期表1、2或3族的元素、或卤素;0<x≤1;1≤y≤3;1≤z≤8);锂金属;锂合金;硅基合金;锡基合金;金属氧化物,例如SnO、SnO2、PbO、PbO2、Pb2O3、Pb3O4、GeO、GeO2、Bi2O3、或Bi2O5;导电聚合物,例如聚乙炔;Li-Co-Ni基材料;钛氧化物;或锂钛氧化物。
对于导电材料、粘合剂和填料的描述与用于正极的导电材料、粘合剂和填料相同,因此省略。
隔板防止正极和负极之间的短路,且提供了锂离子的迁移路径。隔板可包括具有高离子渗透性和机械强度的绝缘薄膜。隔板的具体例可以是包括聚丙烯或聚乙烯或含聚丙烯和聚乙烯的多层膜的聚烯烃基聚合物膜、多孔膜、或是织物或无纺布。当诸如聚合物之类的固体电解质在用作电解质时,固体电解质也可用作为隔板。
接着,在本发明一实施方式中所包括的电池壳体120构造为容纳电极组件110。电池壳体120可以是袋型电池壳体。电池壳体120可具有单层结构或多层结构。
当电池壳体120具有单层结构时,其必需是由电流不能通过的绝缘材料形成。由于电池壳体120与引线端子140直接接触,将在下文描述,所以当密封时,唯有绝缘材料防止了电池壳体120和引线端子140之间的短路,并无单独的绝缘组件,并且即使当电极组件110和电池壳体120由于外部冲击而彼此直接接触时,也不会发生短路。绝缘材料的具体例可以为聚乙烯或聚丙烯。当电池壳体120具有单层结构时,与多层结构相比,单层结构具有更低的生产成本,不需要层压工艺,并因此制备方法简单。
另一方面,当电池壳体120具有多层结构时,多层结构可包括铝层、位于铝层的一个表面上的外层、以及位于铝层的另一表面上的内层。外层和内层的材料可以相同或者彼此不同,并且可以为电流不能流过的绝缘材料。构成外层和内层的材料的具体例可包括聚丙烯(PP)、双向拉伸的尼龙(ONY)、聚对苯二甲酸乙二醇酯(PET)、聚对苯二甲酸丁二醇酯、共聚物酯、或聚碳酸酯。此外,在铝层和外层之间、以及在铝层和内层之间可进一步包括单独的粘结层。
接着,在根据本发明的一个实施方式的锂二次电池中所包括的表层130是位于电池壳体120的外侧的整个表面上。由于表层130包含工程塑料,所以表层130起到防止电解液从电池壳体120泄漏到外面的作用,并起到防止外部湿气渗透到电池壳体120内的作用,也就是说,表层130起到将电池壳体120密封起来的作用。另外,由于表层130取代了通常用于密封电池壳体的铝层而起到密封电池壳体的作用,因此包括该表层的锂二次电池的电池壳体不再需要包括铝层。因此,由于铝层所导致的电池壳体内的短路问题可得到解决,该锂二次电池具有优异的绝缘性。
当电池壳体120不包括铝层,并且是具有由绝缘材料形成的单层结构时,表层130可以位于覆盖电池壳体120的外侧的整个表面以密封电池。即使当电池壳体120具有含铝层的多层结构时,表层130可以位于覆盖电池壳体120的外侧的整个表面以增强密封性。进一步地,不考虑电池壳体120的结构,表层130可以位于具有围绕除了引线端子140之外的电池壳体120的结构,下文将要描述。
表层130可以具有1至10μm的厚度,优选2至7μm,更优选3至5μm。当满足上述厚度时,电解液的泄漏和外部湿气的渗入可以得到防止。
工程塑料可以为选自由以下所构成的组中的至少一种或两种:聚酰胺(PA)、聚缩醛(POM)、聚碳酸酯(PC)、改性聚苯醚(PPE)、聚对苯二甲酸丁二醇酯(PBT)、GF-增强的聚对苯二甲酸乙二醇酯(GF-PET)、超高分子量聚乙烯(UHPE)、聚砜(PSF)、聚醚砜(PES)、聚苯硫醚(PPS)、聚芳酯(PAR)、聚酰胺酰亚胺(PAI)、聚醚酰亚胺(PEI)、聚醚醚酮(PEEK)、聚酰亚胺(PI)、液晶聚酯(LCP)、聚四氟乙烯(PTEE)、聚氨基双马来酰亚胺(polyaminobismaleimide,PABM)、聚双酰胺三唑(polybisamidetriazole,BT)。特别地,工程塑料可以为聚酰胺酰亚胺。
接着,本发明的锂二次电池100可包括电解质(未示出)。电解质可以为含锂盐的非水电解质。锂盐可以为例如LiCl、LiBr、LiI、LiClO4、LiBF4、LiB10Cl10、LiPF6、LiCF3SO3、LiCF3CO2、LiAsF6、LiSbF6、LiAlCl4、CH3SO3Li、(CF3SO2)2NLi、低级脂肪族锂羧酸盐、四苯基锂硼酸盐、或酰亚胺。
非水电解质并不特别受限,只要其用于电池中即可,但是非水电解质的具体例可以为非水液体电解质、有机固体电解质、或无机固体电解质。在本发明中,优选使用有机固体电解质,其为聚合物电解质。有机固体电解质的具体例可以为聚乙烯的衍生物、聚环氧乙烷的衍生物、聚环氧丙烷的衍生物、磷酸酯聚合物、聚活化赖氨酸(poly agitationlysine)、聚酯硫醚、聚乙烯醇、聚偏二氟乙烯或含有离子离解基团的聚合物。
接着,在本发明的锂二次电池100中所包含的引线端子140与电极组件110连接,并引出至袋型电池壳体120之外。表层130可以不位于或者部分地位于引线端子140的表面上。引线端子140中的一个是指与负极电连接的负极引线端子,另一个是指与正极电连接的正极引线端子。引线端子140和电极组件110可以通过电阻焊、超声焊或激光焊而电连接。接片可进一步位于引线端子140和电极组件110之间。
图3是示出根据本发明的另一实施方式的表层230的图。参照图3,表层230位于电池壳体120的外侧的部分区域,其为包括密封部的部分区域。在这种情况下,电池壳体120可具有含铝层的多层结构。这是因为,当电池壳体120具有仅仅由绝缘材料形成的单层结构时,电池壳体自身的密封性能很低。因此,当使用具有一定密封性的、含铝层的多层结构的电池壳体120时,表层230可以仅仅位于电池壳体120的部分区域。
在下文,将描述根据本发明的锂二次电池的制备方法。
根据本发明的锂二次电池的制备方法包括:在容纳电极组件的电池壳体120的外侧上形成包含工程塑料的表层,以便将引线端子140引出至电极组件110之外。
形成表层的步骤可包括:第一步骤,将电池壳体浸涂于包含工程塑料的溶液中;以及第二步骤,将经浸涂的电池壳体于170-190℃干燥2-4小时,以形成表层。
表层可以形成于电池壳体的外侧的整个表面上,以及可以形成在包括电池壳体的密封部的部分区域上。工程塑料的具体例与如上所述的相同,溶剂的具体例可以为二甲亚砜、环己基亚砜、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基-2-吡咯烷酮、N-甲基-2-吡咯烷酮、1,3-二甲基-2-咪唑烷酮或环丁砜。
根据本发明的锂二次电池的制备方法还可包括:在第一步骤之前,通过于180-195℃在0.30-0.50MPa的压力下热粘结2-4秒来将电池壳体进行密封。当进一步包括所述的密封步骤时,在上述浸涂工艺中电解质泄露的意外事故可得以防止。而且,由热粘结所导致的短路可得以防止。
同时,本发明的锂二次电池可以用于包括单元电池的电池模块、包括该电池模块的电池组、以及采用该电池组作为电源的装置。所述装置的具体例可以是但不局限于:电动马达驱动的电动工具;包括电动车(EV)、混合动力车(HEV)、插电式混合动力车(PHEV)等在内的的电动汽车;包括E-自行车和E-踏板车在内的电动两轮车;电动高尔夫球车;电力存储系统等。
在下文中,将提供示例性实例来帮助理解本发明。然而,对于本领域普通技术人员来说显而易见的是,本发明的上述描述是示例性的,并且本文公开的示例性实施方式可以容易地修改成其他具体形式,而不改变本发明的技术精神或实质特征,并且这些变形和修改应在所附权利要求的范围内。
实施例1
用于涂布表层的溶液的制备
将25克聚酰胺酰亚胺(PAI)加入到80ml N,N-二甲基乙酰胺,并于室温下搅拌24小时使其溶解,由此制得包含25重量%聚酰胺酰亚胺的涂布溶液。
正极的制造
制备200g由92重量%作为正极活性材料的锂钴复合氧化物、4重量%作为导电材料的碳黑和4重量%作为粘合剂聚合物的聚偏二氟乙烯(PVDF)构成的混合物,将其加入到220ml作为溶剂的N-甲基-2-吡咯烷酮(NMP)中,由此制备正极混合物浆料。通过将该正极混合物浆料涂覆到正极集电器的20μm厚的铝薄膜上并将该涂覆的正极混合物浆料干燥,然后在其上进行辊压来制造正极。
负极的制造
制备200g由96重量%作为负极活性材料的碳粉、1重量%作为导电材料的碳黑和3重量%作为粘合剂聚合物的PVDF构成的混合物,然后将其加入到220ml作为溶剂的NMP中,由此制备负极混合物浆料。通过将该负极混合物浆料涂覆到作为负极集电器的10μm厚的铜薄膜上并将该涂覆的负极混合物浆料干燥,然后在其上进行辊压来制造负极。
电池的制造
通过将以上制得的正极和负极、以及聚乙烯隔板进行堆叠来制造电极组件。电极组件和引线端子(铝(A1050)-镍-铜(C1100,在其表面上镀有1μm厚的镍))通过超声焊进行连接。将电极组件容纳于具有聚丙烯单层结构的袋型电池壳体内,并将其设置为引线端子引出至电池壳体之外,然后将电池壳体组装起来。接下来,将电解液(碳酸乙烯酯(EC)/碳酸甲乙酯(EMC)=1/2(体积比)、1摩尔六氟磷酸锂(LiPF6))注入到电池壳体内。使用夹具将电池壳体固定后,用涂布溶液浸涂电池壳体到3μm的厚度,并且于177℃干燥3小时,由此完成电池。
实施例2
如实施例1所述制备电极组件,然后将与实施例1所用相同的引线端子与该电极组件连接。将该电极组件容纳在具有PP/Al/ONY/PET结构的袋型电池壳体中,并设置为引线端子引出至电池壳体之外,然后组装电池壳体。接下来,将30g电解液(EC/EMC=1/2(体积比),1摩尔LiPF6)注入到电池壳体中。使用夹具将电池壳体固定后,用涂布溶液浸涂电池壳体到3μm的厚度,并且于177℃干燥3小时,由此完成电池。
实施例3
以与实施例1相同的方式制备电池,只是使用夹具将其间注入有电解液的电池壳体固定,于190℃在0.4MPa下热粘结3秒,以及用涂布溶液进行浸涂。比较例1
如实施例1所述制备电极组件。电极组件和引线端子(铝(A1050)-镍-铜(C1100,在其表面上镀有1μm厚的镍))通过焊接进行连接。在引线端子上形成绝缘部件聚丙烯。将电极组件容纳于具有PP/Al/ONY/PET结构的袋型电池壳体中,并将其设置为引线端子引出至电池壳体之外,然后将电池壳体组装起来。接下来,将30g电解液(EC/EMC=1/2(体积比),1摩尔LiPF6)注入到电池壳体内。之后,通过于190℃在0.4MPa下热粘结3秒而将电池壳体密封,从而完成电池。
比较例2
以与比较例1相同的方式制备电池,只是电池壳体的热粘结是于210℃在0.5MPa下进行。
实验例
密封性评价
实施例1、2、3和比较例1的电池在60℃和90%湿度下存储32周,然后评价每个锂二次电池的密封性。
首先,视觉观察实施例1、2、3和比较例1的每个电池,检查是否有电解质泄漏出电池。实施例1、2、3和比较例1中的任一电池均没有电解质泄漏出电池的迹象。
测量在实施例1、2、3和比较例1的每个电池中电解液的氟化氢(HF)浓度。
在实施例1、2、3的电池中,在电解液中没有检测到HF,但是在比较例1的电池中,在电解液中检测到HF浓度为6.7%。因此,可以表明外部湿气已经渗透进入该电池。
※当电解液含有LiPF6锂盐时,LiPF6必定是以Li+和PF6 -的形式存在。然而,当偶然地发生副反应时,得到不稳定的PF5作为副产物,其与H2O反应以生成HF。因此,需要检查电解液中HF浓度以评价外部湿气是否已渗透入电池中。
绝缘性评价
将实施例1、2、3的电池置于比较例2的电池的密封条件下,即,于210℃在0.5MPa下3秒,然后评价是否在每个电池中发生介质击穿。
尽管根据本发明各实施例的锂二次电池没有介质击穿,但是比较例2的锂二次电池发生了短路,这是因为在热粘接期间绝缘部件的聚丙烯和电池壳体内层的聚丙烯发生熔融,并因此引线端子与电池壳体的铝层接触。更具体地说,在暴露的铝和单个引线端子之间的电阻为100mΩ,并且由于介质击穿,发生电解质的电化学氧化反应,并由此电池膨胀。
本发明的锂二次电池由于位于电池壳体的外侧的表层而具有优异的密封性,因此电解液不会泄漏出电池之外,并且外部湿气不会渗透到电池内。
由于本发明的锂二次电池因表层而具有优异的密封性,因此,不必需采用含铝层的多层电池壳体。因此,由于本发明的锂二次电池可以采用由绝缘材料组成的电池壳体,尽管该电池壳体与引线端子直接接触,但是不存在短路的风险,由此锂二次电池具有优异的密封性。
由于本发明的锂二次电池采用浸涂法而不是热粘接法去密封电池壳体,锂二次电池不需要昂贵的设备,由此生产成本得以降低。
与具有包括常规铝层的多层结构的电池壳体相比,在本发明的锂二次电池中,电池壳体可以具有由电流不能通过的绝缘材料形成的单层结构,电池壳体不需要层压工艺。因此,本发明的制备锂二次电池的方法比制备锂电池的常规方法更为简单。
对于本领域技术人员显而易见的是,在不偏离本发明的精神或范围的情况下,可以对本发明的上述示例性实施方式进行各种修改。因此,本发明旨在涵盖所有这些修改,只要它们在所附权利要求及其等同物的范围内。
Claims (13)
1.一种锂二次电池,包括:
电极组件;
电池壳体,构造为容纳所述电极组件;
包含工程塑料的表层,位于电池壳体外侧上;和
引线端子,连接到所述电极组件并引出至所述电池壳体之外。
2.如权利要求1所述的锂二次电池,其中所述电池壳体包括袋型电池壳体。
3.如权利要求1所述的锂二次电池,其中所述电池壳体由绝缘材料形成。
4.如权利要求3所述的锂二次电池,其中所述电池壳体具有单层结构。
5.如权利要求3所述的锂二次电池,其中所述绝缘材料为聚乙烯或聚丙烯(PP)。
6.如权利要求1所述的锂二次电池,其中所述电池壳体具有多层结构,所述多层结构包括铝层、位于所述铝层的一个表面上的外层、以及位于所述铝层的另一表面上的内层。
7.如权利要求1所述的锂二次电池,其中所述表层位于所述电池壳体的外侧的整个表面上。
8.如权利要求1所述的锂二次电池,其中所述表层位于所述电池壳体的外侧的部分区域上。
9.如权利要求1所述的锂二次电池,其中所述工程塑料包括由以下所构成的组中的至少一个或两个:聚酰胺(PA)、聚缩醛(POM)、聚碳酸酯(PC)、改性聚苯醚(PPE)、聚对苯二甲酸丁二醇酯(PBT)、GF-增强的聚对苯二甲酸乙二醇酯(GF-PET)、超高分子量聚乙烯(UHPE)、聚砜(PSF)、聚醚砜(PES)、聚苯硫醚(PPS)、聚芳酯(PAR)、聚酰胺酰亚胺(PAI)、聚醚酰亚胺(PEI)、聚醚醚酮(PEEK)、聚酰亚胺(PI)、液晶聚酯(LCP)、聚四氟乙烯(PTEE)、聚氨基双马来酰亚胺(PABM)、聚双酰胺三唑(BT)。
10.如权利要求1所述的锂二次电池,其中所述锂二次电池包括聚合物电解质。
11.一种制备锂二次电池的方法,包括:在容纳有电极组件的电池壳体的外侧上形成包含工程塑料的表层,以便将与电极组件连接的引线端子引出至电池壳体之外。
12.如权利要求11所述的方法,其中所述形成表层包括:
第一步骤,将电池壳体浸涂在包含工程塑料的溶液中;和
第二步骤,将经浸涂的电池壳体于170-190℃干燥2-4小时,以形成表层。
13.如权利要求12所述的方法,进一步包括:在第一步骤之前,通过于180-195℃在0.3-0.5MPa的压力下热粘合2-4秒来密封电池壳体。
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US11189871B2 (en) | 2021-11-30 |
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KR20170111856A (ko) | 2017-10-12 |
US20170288181A1 (en) | 2017-10-05 |
CN107331801B (zh) | 2020-08-04 |
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