CN103975461B - 具有z字形密封部的二次电池 - Google Patents
具有z字形密封部的二次电池 Download PDFInfo
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- CN103975461B CN103975461B CN201380004169.8A CN201380004169A CN103975461B CN 103975461 B CN103975461 B CN 103975461B CN 201380004169 A CN201380004169 A CN 201380004169A CN 103975461 B CN103975461 B CN 103975461B
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- secondary cell
- battery case
- recess
- battery
- sealing
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- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052732 germanium Inorganic materials 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
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- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
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- 150000002461 imidazolidines Chemical class 0.000 description 1
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- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 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
- 150000002641 lithium Chemical class 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
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 1
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 description 1
- 229910001537 lithium tetrachloroaluminate 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
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- QLOAVXSYZAJECW-UHFFFAOYSA-N methane;molecular fluorine Chemical compound C.FF QLOAVXSYZAJECW-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
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- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical group C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
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- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
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- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical group O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 229920005608 sulfonated EPDM Polymers 0.000 description 1
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- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 1
- BHZCMUVGYXEBMY-UHFFFAOYSA-N trilithium;azanide Chemical compound [Li+].[Li+].[Li+].[NH2-] BHZCMUVGYXEBMY-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明提供一种二次电池,其中电极组件容纳在电池壳中,其中所述电池壳由包含树脂层和金属层的层压片制成,且通过在容纳所述电极组件的状态下密封其外周表面而被密封,并且在所述电池壳的所述外周表面处的密封部中的至少一个设置有至少两个连续形成的凹进部。
Description
技术领域
本发明涉及一种包含Z字形密封部的二次电池,并且更加特别地涉及一种其中电极组件容纳在电池壳中的二次电池,其中电池壳由包含树脂层和金属层的层压片制成且通过在容纳电极组件的状态下密封其外周表面而被密封,并且在电池壳的外周表面处的密封部中的至少一个设置有至少两个连续形成的凹进部。
背景技术
随着移动装置技术继续发展并且对其的需求继续增加,对于作为能源的电池的需求正在快速地增加。因此,对于可以满足各种需要的电池的各种研究已经在进行中。
另外,因为近来对于环境问题的关注正在增加,所以对于能够替代作为空气污染的主要原因之一的、使用化石燃料的车辆如汽油车辆、柴油车辆等的电动车辆(EV)、混合EV(HEV)等的研究正在积极进行中。作为EV、HEV等的电源,主要使用镍金属氢化物二次电池。然而,对于具有高能量密度、高放电电压和输出稳定性的锂二次电池的研究在积极进行中并且某些这样的锂二次电池可商购获得。
虽然锂二次电池具有优异的电特性并且是相对轻质的,但是由于其安全性问题,锂二次电池尚未被广泛地使用。为了增强这种锂二次电池的安全性,已经尝试使用正温度系数元件、温度保险丝、减压保护电路等以防止温度的增加。
然而,虽然这些锂二次电池包含上述元件,但是在异常条件下可能由于电池内部的异常反应而产生气体。
当前制造的二次电池基本上具有内部真空结构。这种结构旨在通过从电池的内部移除反应性气体而抑制潜在的副反应。然而,由于这点,当在异常条件下产生气体时,二次电池会被大量的气体填充,直至将气体排放到外部并且其排放时间延迟,这增加了二次电池爆炸的风险。
因此,为了解决上述问题,如图1到3中所示,常规上已经尝试了在电池壳的密封部处形成通风孔部。
特别地,参考图1到3,在设置在电池单元10、20或30的电池壳14一侧的密封部处形成通风孔部15、25或35。
图1的电池单元10的通风孔部15具有从电池壳14的内部朝向外部凹进的形状。图2的电池单元20的通风孔部25具有修改的宽度。图3的电池单元30的通风孔部35具有其中杂质等嵌入密封部中的结构。
通风孔部15、25和35具有如下结构:当电池壳14的内部压力增加时,通风孔部15、25和35由于集中在其上的应力而破裂并且因此将在电池壳14内部产生的气体排放到外部。因此,根据使得通风孔部破裂的临界压力来确定具有这种结构的通风孔部的具体尺寸。然而,图1到3中分别示出的通风孔部15、25和35具有可能因在充放电期间发生的、电池单元10、20和30的膨胀和收缩而容易地被损坏的结构。另外,即使当根据临界压力将通风孔部设计成具有特定尺寸时,通风孔部仍可能在达到临界压力之前破裂,因为如上所述通风孔部可能容易被损坏。
因此,非常迫切的需要开发一种二次电池,该二次电池可以与其中电池单元的内部压力达到临界压力的情况一致地被准确地通风。
发明内容
技术问题
本发明旨在解决相关技术的前述问题并且实现长期以来追求的技术目标。
特别地,本发明的一个目的在于提供一种二次电池,所述二次电池通过在电池壳的外周表面处的密封部处连续地形成凹进部而具有增强的安全性并且具有在二次电池的内部压力达到临界压力时可以可靠地排放气体的结构。
另外,本发明的另一个目的在于提供一种二次电池,所述二次电池通过以如下方式减少爆炸的风险而具有增强的安全性:使得当异常运行条件不是相对严重时使电池壳通风并且因此由其排放内部气体。
技术方案
根据本发明的一个方面,提供一种二次电池,
其中电极组件容纳在电池壳中,
其中所述电池壳由包含树脂层和金属层的层压片制成且通过在容纳所述电极组件的状态下密封其外周表面而被密封,并且
在所述电池壳的所述外周表面处的密封部中的至少一个设置有至少两个连续形成的凹进部。
如上所述,常规的通风孔部具有可能因在电池单元的充放电期间发生的、电池单元的膨胀和收缩而容易地被损坏的结构与其中内部压力和应力仅集中于其特定区域上的结构。因此,具有上述结构的通风孔部可能更早地破裂,虽然它们没有达到临界压力,并且因此通风孔部的总体运行可靠性低。
相比之下,在根据本发明的二次电池中,连续地形成至少两个凹进部并且因此在内部产生的压力可以分布到凹进部。因此,当二次电池的内部压力达到临界压力时,可以与其一致地准确地安全地进行气体排放。
特别地,根据本发明的电池壳由包含树脂层和金属层的层压片制成并且这种材料具有其中层压片的外周表面的密封部因电池单元的重复膨胀和收缩,即,外力的重复施加而变形或断裂或具有减小的刚性的疲劳断裂性质。而且,设计成具有比其它密封部更弱的结构从而由于内部压力而通风的通风孔部具有其中这种疲劳断裂现象被促进的结构。因此,即使根据临界压力将通风孔部设计成具有特定尺寸,具有单一结构的常规通风孔部仍可能因重复的外力而经历疲劳断裂,并且因此,通风孔部可能在比设定的临界压力更低的压力下通风或者在非预期的压力下通风。
然而,根据本发明的电池壳包含具有如下结构的通风孔部:多个凹进部彼此相邻地布置并且因此内部压力或者外力可以分布到凹进部。因此,上述疲劳断裂的发生可以显著地减少并且因此可以使电池壳响应于设定的临界压力而准确地通风。
在一个具体实施方式中,凹进部可以具有如下结构:在电极组件的方向上的边界线上形成在电池壳的外周表面处的密封部并且至少两个凹进部连续地形成为具有Z字形形状。
Z字形形状可以例如是其中当在水平横截面上观看时至少两个多边形彼此相邻或者至少两个半圆形彼此相邻的形状。特别地,Z字形形状不受特别限制,只要该形状使得在电池壳中产生的压力或应力能够分布到凹进部即可。例如,Z字形形状可以是其中至少两个三角形、四边形或者椭圆形彼此相邻的形状。
在一个具体实施方式中,连续地形成的凹进部的总长度可以是在外周表面处的密封部的长度的5%~40%,并且凹进部的数目可以是2~10。
特别地,当凹进部的总长度小于在外周表面处的密封部的长度的5%时,难以如上所述在相对低的内部压力下获得气体排放效果。另一方面,当凹进部的总长度超过在外周表面处的密封部的总长度的40%时,密封部的密封力可能减小。
凹进部的凹进深度可以是密封部的宽度的5%~50%,并且凹进部的宽度可以是密封部的宽度的5%~50%。
特别地,当凹进部的凹进深度或者宽度超过密封部的宽度的50%时,密封部的密封力可能减小。另一方面,当凹进部的凹进深度或者宽度小于密封部的宽度的5%时,难以获得期望的效果。
在某些情况中,电池壳可以包含为了使电池壳的内部保持在常压下而注射的惰性气体。
可商购获得的二次电池基本上具有内部真空结构。设计这种结构是为了通过移除电池壳内部的反应性气体而防止各种潜在的副反应。然而,由于这一点,当由于电池的异常反应如过充电等而在二次电池内部产生气体时,在电池被通风之前需要相对长的时间,结果,内部异常反应加剧并且爆炸的风险增加。
相比之下,在其中将惰性气体注射到二次电池中以将其内部保持在常压状态下的情况中,当如上所述的异常反应发生时,二次电池在相对短的时期内具有增加的内部压力,从而被通风。因此,可以防止这种异常反应的加剧并且还可以减小爆炸的风险。
惰性气体可以是不在二次电池内部引起单独的电化学反应的任何气体并且可以例如是选自氦气、氮气和氩气的至少一种气体。
在其制造过程中在移除在为了活化二次电池而进行的初始充放电期间产生的气体之后,可以利用惰性气体填充电池壳。通常,在组装二次电池时在活化过程中产生不会对电池性能作出贡献的气体并且通过单独的过程将其移除。因此,可以在移除在活化过程中产生的气体之后利用惰性气体填充电池壳。
电极组件不受特别限制并且其实例包括卷绕型电极组件、堆叠型电极组件和堆叠/折叠型电极组件。
电极组件具有构成二次电池的正极/隔膜/负极结构。通常,电极组件根据其结构一般地分成两种类型:卷状型(卷绕型)和堆叠型。通过如下制造卷状型电极组件:利用电极活性材料等涂布用作集电器的金属箔,干燥并且挤压涂布的金属箔,将箔切割成具有期望的宽度和长度的带状,使用隔膜将负极与正极分离并且将所得结构螺旋卷绕。这种卷状型电极组件适合在圆筒形电池中使用,但是由于电极活性材料的分离、不良的空间利用等而不适合在矩形电池或者袋型电池中使用。相比之下,堆叠型电极组件具有其中多个正极和负极单元依次堆叠的结构并且易于具有矩形形状,但是不利之处在于制造过程复杂,并且因为在对其施加冲击时电极受到推动,所以引起短路。
为了解决这些问题,作为卷状型电极组件和堆叠型电极组件的组合的先进的电极组件,已经开发了具有如下结构的电极组件:使用长的连续隔离膜折叠具有特定单元尺寸的正极/隔膜/负极结构的全电池或者具有特定单元尺寸的正极(负极)/隔膜/负极(正极)/隔膜/正极(负极)结构的双电池,并且将这种电极组件称作堆叠/折叠型电极组件。
全电池具有其中正极和负极设置在单电池的相反侧的正极/隔膜/负极的单元结构。全电池的实例包括但不限于正极/隔膜/负极单电池(最基本的结构)和正极/隔膜/负极/隔膜/正极/隔膜/负极单电池。
双电池具有其中相同的电极设置在单电池的相反侧的正极/隔膜/负极/隔膜/正极的单元结构或者负极/隔膜/正极/隔膜/负极的单元结构。在本说明书中,将具有正极/隔膜/负极/隔膜/正极结构的双电池表示为“C型双电池”,并且将具有负极/隔膜/正极/隔膜/负极结构的双电池表示为“A型双电池”。即,将其中正极设置在电池的相反侧的双电池称作C型双电池,并且将其中负极设置在电池的相反侧的双电池称作A型双电池。
构成这些双电池的正极、负极和隔膜的数目不受特别限制,只要设置在双电池的相反侧的电极具有相同的结构即可。
通过在正极和负极之间设置隔膜并且将这些元件相互结合而制造全电池和双电池。结合过程可以例如是热熔合。
如上所述,电池壳由包含树脂层和金属层的层压片制成并且与由金属材料制成的电池壳相比,这种层压片可以更加减小二次电池的重量。另外,用作移动产品或者中型和大型装置的电源的二次电池必须是轻质的。根据本发明,通过在其中将电极组件容纳在电池壳中的状态下密封其外周表面,将电池壳密封。
在一个示例性实施方式中,层压片可以具有包含外部树脂层、阻挡空气和湿气的金属层、以及内部热熔合树脂层的堆叠结构。
外部树脂层必须具有高的外部环境耐受性,因此要求预定水平以上的抗拉强度和耐候性。在这方面,外部涂层的聚合物树脂可以包含聚萘二甲酸乙二醇酯(PEN)、聚对苯二甲酸乙二醇酯(PET)或者显示高抗拉强度和耐候性的取向尼龙。
另外,外部涂层可以由PEN形成和/或可以在其外表面处设置有PET层。
与PET相比,即使在小的厚度下,PEN仍具有高的抗拉强度和耐候性,并且因此适合在外部涂层中使用。
内部树脂层的聚合物树脂可以是具有热熔合性质(热粘附性质)且相对于电解质的吸湿性低以防止电解质的渗透并且不因电解质而膨胀或沉积的聚合物树脂。更特别地,内部树脂层的聚合物树脂可以是氯化聚丙烯(CPP)膜。
在一个示例性实施方式中,根据本发明的层压片可以包含具有5μm~40μm的厚度的外部涂层、具有20μm~150μm的厚度的阻挡层和具有10μm~50μm的厚度的内部密封剂层。当层压片的各层的厚度太小时,难以预期材料的阻挡性能和强度的增强。另一方面,当层压片的各层的厚度太大时,可加工性劣化并且层压片的厚度增加。
二次电池可以是具有其中包含正极、负极和设置在其间的隔膜的电极组件被含锂盐的非水电解质浸渗的结构的锂二次电池。
可以通过例如在正极集电器上涂布包含正极活性材料的正极混合物并且干燥经涂布的正极集电器而制造正极。根据需要,正极混合物可以进一步选择性地包含粘合剂、导电材料、填料等。
正极集电器通常被制造为3~500μm的厚度。正极集电器不受特别限制,只要其不在所制造的锂二次电池中引起化学变化并且具有高的导电性即可。例如,正极集电器可以由不锈钢,铝,镍,钛,烧结碳,利用碳、镍、钛或银等表面处理过的铝或不锈钢制成。正极集电器可以在其表面处具有微细的不规则以增加正极活性材料和正极集电器之间的粘附。另外,正极集电器可以以包括膜、片、箔、网、多孔结构、泡沫和无纺布的各种形式中的任何一种形式使用。
正极活性材料是能够诱导电化学反应的材料并且是包含至少两种过渡金属的锂过渡金属氧化物。锂过渡金属氧化物的实例包括但不限于:被一种或者多种过渡金属置换的层状化合物如锂钴氧化物(LiCoO2)和锂镍氧化物(LiNiO2);被一种或者多种过渡金属置换的锂锰氧化物;由式LiNi1-yMyO2表示的锂镍基氧化物,其中M是Co、Mn、Al、Cu、Fe、Mg、B、Cr、Zn和Ga中的至少一种并且0.01≤y≤0.7;由式Li1+zNibMncCo1-(b+c+d)MdO(2-e)Ae表示的锂镍钴锰复合氧化物,其中-0.5≤z≤0.5,0.1≤b≤0.8,0.1≤c≤0.8,0≤d≤0.2,0≤e≤0.2,b+c+d<1,M=Al、Mg、Cr、Ti、Si或Y,并且A=F、P或Cl,诸如Li1+zNi1/3Co1/3Mn1/3O2和Li1+ zNi0.4Mn0.4Co0.2O2;和由式Li1+xM1-yM’yPO4-zXz表示的橄榄石基锂金属磷酸盐,其中M是过渡金属,特别地Fe、Mn、Co或Ni,M’是Al、Mg或Ti,X是F、S或N,-0.5≤x≤+0.5,0≤y≤0.5,并且0≤z≤0.1。
基于包含正极活性材料的混合物的总重量,典型地以1到30重量%的量添加导电材料。对于导电材料没有特别限制,只要其不在所制造的电池中引起化学变化并且具有导电性即可。导电材料的实例包括石墨如天然石墨或人造石墨;碳黑如碳黑、乙炔黑、科琴黑、槽法炭黑、炉黑、灯黑和热裂法炭黑;导电纤维如碳纤维和金属纤维;金属粉末如氟化碳粉末、铝粉末和镍粉末;导电晶须如氧化锌和钛酸钾;导电金属氧化物如二氧化钛;和聚苯撑衍生物。
粘合剂是有助于活性材料和导电材料之间的结合和活性材料到集电器的结合的成分。基于包含正极活性材料的混合物的总重量,典型地以1到30重量%的量添加粘合剂。粘合剂的实例包括但不限于: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、聚乙烯基吡咯烷酮、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、氟橡胶和各种共聚物。
填料任选地用作用于抑制正极膨胀的成分。填料不受特别限制,只要其是不在所制造的电池中引起化学变化的纤维材料即可。填料的实例包括烯烃类聚合物如聚乙烯和聚丙烯;和纤维材料如玻璃纤维和碳纤维。
可以通过例如在负极集电器上涂布包含负极活性材料的负极混合物并且干燥经涂布的负极集电器而制造负极。根据需要,负极混合物可以进一步包含上述成分如导电材料、粘合剂、填料等。
负极集电器典型地被制造为3~500μm的厚度。负极集电器不受特别限制,只要其不在所制造的电池中引起化学变化并且具有高导电性即可。例如,负极集电器可以由铜,不锈钢,铝,镍,钛,烧结碳,利用碳、镍、钛或银表面处理过的铜或不锈钢,和铝-镉合金制成。类似于正极集电器,负极集电器也可以在其表面处具有微细的不规则以增强负极集电器和负极活性材料之间的粘附并且以包括膜、片、箔、网、多孔结构、泡沫和无纺布的各种形式使用。
负极活性材料的实例包括碳如硬碳和石墨基碳;金属复合氧化物如LixFe2O3(0≤x≤1),LixWO2(0≤x≤1),SnxMe1-xMe’yOz(Me:Mn、Fe、Pb或Ge;Me’:Al,B,P,Si,I、II和III族元素,或者卤素;0<x≤1;1≤y≤3;并且1≤z≤8);锂金属;锂合金;硅基合金;锡基合金;金属氧化物如SnO、SnO2、PbO、PbO2、Pb2O3、Pb3O4、Sb2O3、Sb2O4、Sb2O5、GeO、GeO2、Bi2O3、Bi2O4和Bi2O5;导电聚合物如聚乙炔;和Li-Co-Ni基材料。
已经在关于正极的说明中提供了关于粘合剂、导电材料和根据需要添加的成分的详细说明。
在某些情况中,可以选择性地添加作为用于抑制负极膨胀的成分的填料。填料不受特别限制,只要其是不在所制造的电池中引起化学变化的纤维材料即可。填料的实例包括烯烃类聚合物如聚乙烯和聚丙烯;和纤维材料如玻璃纤维和碳纤维。
另外,可以进一步选择性地添加其它成分如粘度控制剂、粘附促进剂等或者可以进一步组合添加其两种以上。
粘度控制剂是用于调节电极混合物的粘度从而促进电极混合物成分的混合的过程和在电极集电器上涂布电极混合物的过程的成分,并且基于负极混合物的总重量,可以以30重量%的量添加。粘度控制剂的实例包括但不限于羧甲基纤维素和聚偏二氟乙烯。在某些情况中,上述溶剂也可以用作粘度控制剂。
粘附促进剂是为了增强活性材料和集电器之间的粘附而添加的辅助成分,并且基于粘合剂的重量,可以以10重量%以下的量添加。例如,粘附促进剂可以是草酸、己二酸、蚁酸、丙烯酸衍生物、衣康酸衍生物等。
隔膜设置在正极和负极之间,并且作为隔膜,使用具有高离子渗透性和高机械强度的薄绝缘膜。隔膜通常具有0.01~10μm的孔径和5~300μm的厚度。作为隔膜,例如使用由烯烃聚合物如聚丙烯制成的片或者无纺布;或者具有耐化学性和疏水性的玻璃纤维或聚乙烯。当将固体电解质如聚合物等用作电解质时,固体电解质还可以充当隔膜。
含锂盐的非水电解质由电解质和锂盐组成。电解质可以是非水有机溶剂、有机固体电解质、无机固体电解质等。
非水有机溶剂的实例包括非质子有机溶剂如N-甲基-2-吡咯烷酮、碳酸亚丙酯、碳酸亚乙酯、碳酸亚丁酯、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、碳酸亚丙酯衍生物、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包括但不限于聚乙烯衍生物、聚环氧乙烷衍生物、聚环氧丙烷衍生物、磷酸酯聚合物、聚搅拌赖氨酸(poly agitation lysine)、聚酯硫化物、聚乙烯醇、聚偏二氟乙烯和包含离子解离基团的聚合物。
无机固体电解质的实例包括但不限于:锂的氮化物、卤化物和硫酸盐如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中的材料并且其实例包括但不限于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、四苯基硼酸锂和酰亚胺。
另外,为了提高充电/放电特性和阻燃性,例如,可以将嘧啶、亚磷酸三乙酯、三乙醇胺、环醚、乙二胺、正甘醇二甲醚、六磷酸三酰胺(hexaphosphoric triamide)、硝基苯衍生物、硫、醌亚胺染料、N-取代的唑烷酮、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、三氯化铝等添加到电解质中。如果必要,为了赋予不燃性,电解质可以进一步包含含卤素的溶剂如四氯化碳和三氟乙烯。此外,为了提高高温储存特性,非水电解质可以进一步包含二氧化碳气体、碳酸氟代亚乙酯(FEC)、丙烯磺酸内酯(PRS)等。
在一个实施方式中,可以通过将锂盐如LiPF6、LiClO4、LiBF4、LiN(SO2CF3)2等添加到作为高介电溶剂和环状碳酸盐的EC或PC与作为低粘性溶剂和线性碳酸盐的DEC、DMC或EMC的混合溶剂中来制备含锂盐的非水电解质。
本发明还提供包含所述锂二次电池作为单元电池的电池模块和包含该电池模块的电池组。
该电池组可以用作用于需要高温下的稳定性、长循环特性和高倍率特性的中型和大型装置的电源。
这种中型和大型装置的实例包括但不限于:电动机驱动的电动工具;电动车辆(EV)、混合电动车辆(HEV)、和插电式混合电动车辆(PHEV);电动双轮车辆如电动自行车和电动滑板车;电动高尔夫球车;和用于储存电力的系统。
附图说明
图1~4是常规二次电池的截面图;且
图5~7是根据本发明的实施方式的二次电池的横截面图。
具体实施方式
现在,将参考附图和以下实例更加详细地描述本发明。这些实例仅为了说明本发明而提供并且不应该被解释为限制本发明的范围和主旨。
图4是示出常规二次电池100的结构的截面图。图5是示出根据本发明的一个实施方式的二次电池200A的结构的截面图。
参考图4,通过在电池壳的容纳单元中安设电极组件110而制造二次电池100。电极组件110在其一端设置有从电极组件110延伸到电池壳外部的电极端子120和130。通过经由其外周表面的热熔合形成密封部140而密封电池壳。在从每一个侧面观看时,密封部140都具有矩形形状。
参考图5,根据本发明的实施方式的二次电池200A具有与图4的二次电池100相同的基本结构。在图4和5的二次电池之间的差别仅在于:密封部240在其侧面处设置有其中多个凹进部彼此相邻的Z字形通风孔部250A。在通风孔部250A中,在电极组件210的方向上的边界线具有连续的Z字形形状,因此,当二次电池200A壳体的内部压力增加时,压力被适当地施加到凹进部,由此即使在相对低的压力下也可以由其排放气体。
图6和7是根据本发明其它实施方式的二次电池200B和200C的图。
参考图6和7,二次电池200B和200C具有与图5的二次电池200A相同的基本结构。在图5、6和7的二次电池之间存在的差别仅在于:其中多个凹进部彼此相邻的图6和7的Z字形通风孔部250B和250C具有与图5的通风孔部250A不同的形状。特别地,图6的通风孔部250B具有其中具有半圆形形状的凹进部彼此相邻的结构,并且图7的通风孔部250C具有其中具有四边形形状的凹进部彼此相邻的结构。
在图5到7中分别示出的各通风孔部250A、250B和250C的长度L1、L2和L3可以是密封部的总长度L的5%~40%。各通风孔部250A、250B和250C的宽度W1、W2和W3可以是密封部的宽度W的5%~50%。
本领域技术人员可以以上述内容为基础,在本发明的范围内进行各种应用和变化。
工业实用性
如上所述,在根据本发明的二次电池中,在电池壳的外周表面处的密封部处连续地形成凹进部,并且因此,当二次电池的内部压力达到临界压力时,可以可靠地进行气体排放并且可以增强二次电池的安全性。另外,当异常运行状态不是相对严重时使电池壳通风从而排放内部气体,并且因此,可以减小爆炸等的风险,这导致二次电池的安全性增强。
Claims (14)
1.一种二次电池,其中电极组件容纳在电池壳中,
其中所述电池壳由包含树脂层和金属层的层压片制成,且所述电池壳通过在容纳所述电极组件的状态下密封外周表面而被密封,并且
在所述电池壳的所述外周表面处的密封部中的至少一个设置有至少两个连续形成的凹进部,
其中所述凹进部具有如下结构:在所述电极组件的方向上的边界线上形成有在所述电池壳的所述外周表面处的所述密封部,并且至少两个凹进部连续地形成为具有Z字形形状,
其中所述Z字形形状是其中当在水平横截面上观看时至少两个多边形彼此相邻或者至少两个半圆形彼此相邻的形状,使得在电池壳中产生的压力或应力能够分布到所有凹进部,
其中所述电池壳包含为了使所述电池壳的内部保持在常压下而注射的惰性气体。
2.根据权利要求1所述的二次电池,其中所述连续形成的凹进部的总长度是在所述外周表面处的所述密封部的长度的5%~40%。
3.根据权利要求1所述的二次电池,其中所述凹进部的数目是2~10。
4.根据权利要求1所述的二次电池,其中所述凹进部的凹进深度是所述密封部的宽度的5%~50%。
5.根据权利要求1所述的二次电池,其中所述凹进部的宽度是所述密封部的宽度的5%~50%。
6.根据权利要求1所述的二次电池,其中所述惰性气体是选自氦气、氮气和氩气中的至少一种气体。
7.根据权利要求1所述的二次电池,其中在二次电池的制造过程中在移除为了活化所述二次电池而进行的初始充放电期间产生的气体之后,所述电池壳填充有所述惰性气体。
8.根据权利要求1所述的二次电池,其中所述电极组件为卷绕型、堆叠型或者堆叠/折叠型。
9.根据权利要求1所述的二次电池,其中所述层压片具有包含外部树脂层、阻挡空气和湿气的金属层以及内部热熔合树脂层的堆叠结构。
10.根据权利要求1所述的二次电池,其中所述二次电池是锂二次电池。
11.一种电池模块,包含权利要求1到10中任一项的二次电池作为单元电池。
12.一种电池组,包含权利要求11的电池模块。
13.根据权利要求12所述的电池组,其中所述电池组用作中型和大型装置的电源。
14.根据权利要求13所述的电池组,其中所述中型和大型装置是电动车辆、混合电动车辆、插电式混合电动车辆或用于储存电力的系统。
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