CN105122534A - 包含气体透过膜的锂二次电池 - Google Patents
包含气体透过膜的锂二次电池 Download PDFInfo
- Publication number
- CN105122534A CN105122534A CN201480019723.4A CN201480019723A CN105122534A CN 105122534 A CN105122534 A CN 105122534A CN 201480019723 A CN201480019723 A CN 201480019723A CN 105122534 A CN105122534 A CN 105122534A
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- Prior art keywords
- shell
- lithium secondary
- battery
- secondary battery
- air penetrating
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- 239000012528 membrane Substances 0.000 title abstract 2
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- 239000002184 metal Substances 0.000 claims description 11
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 10
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- 238000000576 coating method Methods 0.000 claims description 10
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- 150000001875 compounds Chemical class 0.000 claims description 8
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- 229910052740 iodine Inorganic materials 0.000 description 1
- 230000010220 ion permeability Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
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- 235000015110 jellies Nutrition 0.000 description 1
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- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 1
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Abstract
本发明提供锂二次电池,其包含:电解质;电极层压体;电池壳,所述电池壳包含其中内置有电解质和电极层压体的空间部,和包围所述空间部的密封部;和气体透过膜。
Description
技术领域
本发明涉及包含气体透过膜的锂二次电池。
背景技术
随着移动装置技术持续发展和其需求不断增加,对作为能源的二次电池的需求正在快速增加。在这些二次电池中,对显示高能量密度和放电电压的锂二次电池的研究正在进行且这样的锂二次电池是市售并且广泛使用的。
通常,二次电池具有如下结构:其中将包含正极、负极和置于其间的隔膜的电极组件以层压或卷绕的形式容纳在由金属罐或层压片制成的电池壳中且将电解质注入其中或者用电解质浸渍电极组件。
这种二次电池中由高电压电池单元构成的袋型二次电池的主要研究主题之一是防止由于在对电池进行活化和使用电池时的气体泄漏而导致电池的性能劣化。例如,在活化期间,二次电池生成大量气体,生成的气体损坏电池壳的密封部并且泄漏到外部。随后,电解质泄漏至损坏的密封部,从而使电池的性能劣化。此外,在使用期间,当电解质由于异常的电池运行状态如超过允许的电流和电压的过充、暴露于高温等而分解且生成气体时,电池如上所述被损坏。
因此,对于开发解决上述问题的新型锂二次电池存在迫切需求。
发明内容
技术问题
因此,已经完成了本发明以解决以上问题和尚未解决的其它技术问题。
本发明旨在提供一种锂二次电池以将在对电池进行活化和使用时生成的气体排放到电池的外部、且防止电解质泄漏。
技术方案
根据本发明的一方面,提供锂二次电池,其包含:
电解质;
电极层压体;
电池壳,所述电池壳包含其中内置有电解质和电极层压体的空间部和包围所述空间部的密封部;以及
气体透过膜。
即,根据本发明的锂二次电池包含气体透过膜,从而在对电池进行活化和使用时,将生成的气体排放到外部、且防止电解质泄漏。
可以将气体透过膜设置在所述空间部中。
所述气体透过膜可以为液体非透过性的。由此,可以防止电解质的泄漏。
气体透过膜的孔径可以为2.0埃~10埃。当孔径小于2.0埃时,可能不会充分地将气体排放到外部。另一方面,当孔径大于10埃时,电解质可能会泄漏。因此,气体透过膜的合适孔径可以在上述范围内。
所述气体透过膜可以为选择性地透过氧气(O2)和二氧化碳(CO2)的选择性气体透过膜。
所述选择性气体透过膜的孔径可以为2.0埃~10埃。当孔径小于2.0埃时,可能不会充分地将氧气和二氧化碳排放到外部。另一方面,当孔径大于10埃时,除氧气和二氧化碳外,电解质可能会泄漏。因此,选择性气体透过膜的合适孔径可以在上述范围内。
气体透过膜可以由聚对苯二甲酸乙二醇酯(PET)构成,但本发明不限于此。
气体透过膜可以在垂直剖面中设置于电极层压体与密封部之间。
气体透过膜可以在垂直剖面中分割空间部。
气体透过膜可以贯通所述密封部。
电池壳可以包含第一壳和通过结合至第一壳而密封电池壳的第二壳,且气体透过膜可以置于第一壳与第二壳之间的界面上。
根据本发明的一方面,提供电池壳,所述电池壳包含第一壳和通过结合至第一壳而密封电池壳的第二壳,其中第一壳和第二壳由包含内部密封层、阻挡层和外部涂层的层压片构成,并且第一壳和第二壳中的至少一者全部或部分地由多孔层压片构成。
多孔层压片可以包含内部多孔密封层、多孔阻挡层和外部多孔涂层,且可以具有2.0埃~10埃的孔径。
内部密封层可以由无取向的聚丙烯构成,阻挡层可以由金属构成,且外部涂层可以由聚对苯二甲酸乙二醇酯构成,但本发明不限于此。
内部多孔密封层可以由无取向的多孔聚丙烯构成,多孔阻挡层可以由多孔金属构成,且外部多孔涂层可以由多孔聚对苯二甲酸乙二醇酯构成,但本发明不限于此。
第二壳可以从第一壳的一部分延伸。
第一壳和第二壳可以为分离的独立构件。
根据本发明的一方面,提供锂二次电池,其包含:
电池壳;
电极层压体,其包含至少一个正极、至少一个负极和层压在所述至少一个正极与所述至少一个负极之间的至少一个隔膜;和
电解质。
锂二次电池可以包含选自由下式(1)表示的化合物和由下式(2)表示的化合物中的至少一种锂过渡金属氧化物作为正极活性材料。
LixMyMn2-yO4-zAz(1)
其中0.9≤x≤1.2,0<y<2且0≤z<0.2;
M为选自如下的至少一种元素:Al、Mg、Ni、Co、Fe、Cr、V、Ti、Cu、B、Ca、Zn、Zr、Nb、Mo、Sr、Sb、W、Ti和Bi;且
A为至少一种一价或二价阴离子。
(1-x)LiM'O2-yAy·xLi2MnO3-y'Ay'(2)
其中M'为MnaMb;
M为选自如下的至少一种:Ni、Ti、Co、Al、Cu、Fe、Mg、B、Cr、Zr、Zn和第Ⅱ周期过渡金属;
A为选自如PO4、BO3、CO3、F和NO3的阴离子中的至少一种;
0<x<1;0<y≤0.02;0<y'≤0.02;0.5≤a≤1.0;0≤b≤0.5;且a+b=1。
锂二次电池可以包含碳系材料和/或Si作为负极活性材料。
锂二次电池可以为锂离子电池、锂离子聚合物电池或锂聚合物电池。
电极可以为正极或负极且可以使用包括以下过程的制造方法制作。
所述制造电极的方法包括:
通过将粘合剂分散或溶解在溶剂中制备粘合剂溶液,
通过将粘合剂溶液与电极活性材料以及导电材料混合制备电极浆料,
将电极浆料涂布在集电器上,
对电极进行干燥;和
将电极压缩至特定的厚度。
在某些情况下,所述方法可以还包括对压缩的电极进行干燥。
粘合剂溶液的制备为通过将粘合剂分散或溶解在溶剂中而制备粘合剂溶液的过程。
粘合剂可以为在本领域中已知的所有粘合剂,特别地,可以为选自如下的一种:氟树脂系粘合剂,包括聚偏二氟乙烯(PVdF)或聚四氟乙烯(PTFE);橡胶系粘合剂,包括丁苯橡胶、丙烯腈-丁二烯橡胶或苯乙烯-异戊二烯橡胶;纤维素系粘合剂,包括羧甲基纤维素(CMC)、淀粉、羟丙基纤维素或再生纤维素;多元醇系粘合剂;聚烯烃系粘合剂,包括聚乙烯或聚丙烯;聚酰亚胺系粘合剂;聚酯系粘合剂;贻贝(mussel)粘合剂和硅烷系粘合剂,或者以上列出的粘合剂中的至少两种的混合物或共聚物。
可以根据粘合剂的种类选择性地使用溶剂,例如有机溶剂如异丙醇、N-甲基吡咯烷酮(NMP)、丙酮等,水等。
在本发明的具体实施方式中,通过将PVdF分散或溶解在N-甲基吡咯烷酮(NMP)中可以制备正极用粘合剂溶液,且通过将丁苯橡胶(SBR)/羧甲基纤维素(CMC)分散或溶解在水中可以制备负极用粘合剂溶液。
通过将电极活性材料和导电材料混合/分散在粘合剂溶液中可以制备电极浆料。在涂布过程中使用之前,可以将制备的电极浆料转移至储存罐并进行储存。为了防止电极浆料变硬,可以在储存罐中对电极浆料持续地进行搅拌。
电极活性材料可以为正极活性材料或负极活性材料。
特别地,正极活性材料可以为层状化合物如锂钴氧化物(LiCoO2)和锂镍氧化物(LiNiO2)或者被一种以上过渡金属置换的化合物;由Li1+yMn2-yO4(其中0≤y≤0.33)表示的锂锰氧化物如LiMnO3、LiMn2O3和LiMnO2;锂铜氧化物(Li2CuO2);钒氧化物如LiV3O8、LiV3O4、V2O5和Cu2V2O7;具有式LiNi1-yMyO2(其中M=Co、Mn、Al、Cu、Fe、Mg、B或Ga且0.01≤y≤0.3)的Ni位点型锂镍氧化物;具有式LiMn2-yMyO2(M=Co、Ni、Fe、Cr、Zn或Ta,且0.01≤y≤0.1)或式Li2Mn3MO8(M=Fe、Co、Ni、Cu或Zn)的锂锰复合氧化物;其中一些Li原子被碱土金属离子置换的LiMn2O4;二硫化合物;Fe2(MoO4)3等,但本发明的实施方式不限于此。
在非限制性实施方式中,电极活性材料可以包含由下式(1)表示的尖晶石结构的锂金属氧化物作为正极活性材料:
LixMyMn2-yO4-zAz(1)
其中0.9≤x≤1.2,0<y<2且0≤z<0.2,
M为选自如下的至少一种元素:Al、Mg、Ni、Co、Fe、Cr、V、Ti、Cu、B、Ca、Zn、Zr、Nb、Mo、Sr、Sb、W、Ti和Bi,且
A为至少一种一价或二价阴离子。
A的最大取代量可以为小于0.2摩尔%,特别地,A可以为选自卤素如F、Cl、Br和I,S和N中的至少一种阴离子。
由于这些阴离子的取代,增加了阴离子与过渡金属之间的键合强度,防止了式(1)的化合物的结构转变,因此可以提高锂二次电池的寿命。另一方面,当A的取代量太大(t≥0.2)时,锂二次电池的寿命特性可能会因式(1)化合物的晶体结构不稳定而相当地劣化。
特别地,式(1)的尖晶石结构的锂金属氧化物可以为由下式(1a)表示的锂金属氧化物:
LixNiyMn2-yO4(1a)
其中0.9≤x≤1.2且0.4≤y≤0.5。
更具体地,所述锂金属氧化物可以为LiNi0.5Mn1.5O4或LiNi0.4Mn1.6O4。
负极活性材料可以还包含例如碳如硬碳、石墨系碳等;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,第I、II和III族元素,或者卤素;0<x≤1;1≤y≤3;且1≤z≤8);锂金属;锂合金;硅系合金;锡系合金;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等;Li-Co-Ni系材料;等。
在非限制性实施方式中,电极活性材料可以包含锂金属氧化物作为负极活性材料,其中所述锂金属氧化物可以由下式(3)表示:
LiaM’bO4-cAc(3)
其中M’为选自如下的至少一种元素:Ti、Sn、Cu、Pb、Sb、Zn、Fe、In、Al和Zr;
0.1≤a≤4且0.2≤b≤4,其中根据M’的氧化数来确定a和b;
0≤c<0.2,其中根据A的氧化数来确定c;且
A为至少一种一价或二价阴离子。
式(3)的锂金属氧化物可以由下式(4)表示:
LiaTibO4(4)
其中0.5≤a≤3且1≤b≤2.5。
锂金属氧化物的实例包括但不限于Li0.8Ti2.2O4、Li2.67Ti1.33O4、LiTi2O4、Li1.33Ti1.67O4和Li1.14Ti1.71O4。
在非限制性实施方式中,所述锂金属氧化物可以为Li1.33Ti1.67O4或LiTi2O4。Li1.33Ti1.67O4具有尖晶石结构,所述尖晶石结构在充放电期间的晶体结构变化小且具有高可逆性。
可以使用本领域内已知的制造方法例如固态反应、水热法、溶胶凝胶法等制备所述锂金属氧化物。
锂金属氧化物可以为其中一次粒子相互团聚的二次粒子形式。
二次粒子的直径可以为200nm~30μm。
当二次粒子的直径小于200nm时,在制备负极浆料的过程中需要大量的溶剂,因此降低了生产率且难以控制水分的量。当二次粒子的直径超过30μm时,锂离子的扩散速率变慢,因此可能难以实现高输出。
基于负极活性材料的总重量,锂金属氧化物的量可以为50重量%~100重量%。
其中基于负极活性材料的总重量锂钛氧化物的量为100重量%的情况意味着负极活性材料由锂钛氧化物单独形成。
导电材料没有特别限制,只要其具有导电性且在制造的电池中不引起化学变化即可。导电材料的实例包括:石墨如天然石墨或人造石墨;炭黑如炭黑、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、铝粉和镍粉;导电晶须如氧化锌和钛酸钾;导电金属氧化物如二氧化钛;以及聚亚苯基衍生物。
根据需要,电极浆料可以还任选地包含填料等。填料没有特别限制,只要其为在制造的电池中不引起化学变化的纤维材料即可。填料的实例包括烯烃系聚合物如聚乙烯和聚丙烯;以及纤维材料如玻璃纤维和碳纤维。
电极浆料的涂布为通过使电极浆料经过涂布机头而以预定的图案将电极浆料涂布在集电器上并且涂布至均一厚度的过程。
可以通过如下实施电极浆料的涂布:将电极浆料施加至集电器并且使用刮刀将电极浆料均匀地分散在集电器上。在另一个实施方式中,可以通过压铸、逗号涂布(commacoating)、丝网印刷等进行所述涂布过程。在另一个实施方式中,可以在单独的基底上将电极浆料成型,然后通过压制或层压将其附着至集电器。
集电器没有特别限制,只要其在制造的二次电池中不引起化学变化且具有高导电性即可。例如,集电器可以由如下制成:铜,不锈钢,铝,镍,钛,烧结碳,用碳、镍、钛、银等表面处理的铜或不锈钢,或者铝-镉合金。正极集电器可以在其表面处具有微小的不规则处以提高正极活性材料与正极集电器之间的粘附性,且可以以包括膜、片、箔、网、多孔结构、泡沫和无纺布的各种形式的任一种使用。特别地,正极集电器可以为金属集电器如Al集电器,负极集电器可以为金属集电器如Cu集电器。电极集电器可以为金属箔如Al箔或Cu箔。
干燥过程是从电极浆料中去除溶剂和水分以干燥涂布在金属集电器上的电极浆料的过程。在具体实施方式中,在50℃~200℃的真空烘箱中进行一天以下的干燥过程。
电极制造方法可以还包括在干燥过程之后的冷却过程。可以通过缓慢地冷却至室温来进行冷却过程,使得令人满意地形成粘合剂的再结晶结构。
为了提高完成涂布的电极的容量密度并且提高集电器与相应活性材料之间的粘附性,可以通过使电极经过两个高温加热的辊之间而将电极压缩至所需厚度。这一过程被称为轧制过程。
在使电极经过两个高温加热的辊之间之前,可以对电极进行预加热过程。预加热过程为在使电极通过所述辊之间之前对电极进行预加热以便提高电极的压缩效果的过程。
可以在等于或大于粘合剂的熔点的温度范围内,在50℃~200℃的真空烘箱中将完成轧制的电极干燥一天以下。可以将轧制的电极切割成均一的长度且然后进行干燥。
在干燥过程之后,可以进一步实施冷却过程。可以通过缓慢地冷却至室温来进行冷却过程,使得令人满意地形成粘合剂的再结晶结构。
共聚物层为将正极与负极分开的隔膜,且当将固体电解质如聚合物等用作电解质时,固体电解质也可以充当隔膜。
隔膜可以为具有高离子渗透性和机械强度的绝缘薄膜。隔膜的孔径通常为0.01μm~10μm且其厚度通常为5μm~300μm。
作为隔膜,可以使用由烯烃聚合物如聚丙烯制成的片或无纺布;玻璃纤维或聚乙烯,其具有耐化学性和疏水性;牛皮纸等。市售隔膜包括Celgard型产品(2400、2300(HoechestCelanese公司))、聚丙烯隔膜(宇部工业有限公司或PallRAI)、聚乙烯型隔膜(Tonen或Entek)等。
在某些情况下,可以用凝胶聚合物电解质对隔膜进行涂布以便提高锂二次电池的稳定性。凝胶聚合物的实例包括但不限于聚环氧乙烷、聚偏二氟乙烯和聚丙烯腈。
电极层压体的实例包括本领域中已知的果冻卷型电极组件(或卷绕型电极组件)、层压的电极组件以及层压的且折叠的电极组件。
如在本文中使用,层压的且折叠的电极组件可以被理解为包括通过如下制造的层压的且折叠的电极组件:将单元电池布置在隔膜片上并且将所述隔膜片折叠或卷绕,所述单元电池具有其中隔膜被置于正极与负极之间的结构。
此外,电极层压体可以包括如下的电极层压体:其中通过热结合对具有置于隔膜之间的正极和负极中的任一种的结构以堆叠的状态进行层压。
电解质可以为非水电解质、有机固体电解质、无机固体电解质等。
非水电解质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、碳酸甲乙酯、γ-丁内酯、1,2-二甲氧基乙烷、1,2-二乙氧基乙烷、四氢呋喃、2-甲基四氢呋喃、二甲基亚砜、1,3-二氧戊环、4-甲基-1,3-二烯、二乙醚、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、丙酸乙酯等。
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(polyagitationlysine)、聚酯硫化物、聚乙烯醇、聚偏二氟乙烯和含有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(Li)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、Li3PO4-Li2S-SiS2。
锂盐是易溶于非水电解质中的材料且其实例包括但不限于LiCl、LiBr、LiI、LiClO4、LiBF4、LiB10Cl10、LiPF6、LiCF3SO3、LiCF3CO2、LiAsF6、LiSbF6、LiAlCl4、CH3SO3Li、CF3SO3Li、LiSCN、LiC(CF3SO2)3、(CF3SO2)2NLi、氯硼烷锂、低级脂族羧酸锂、四苯基硼酸锂和亚氨基锂。
此外,为了提高充放电特性和阻燃性,例如,可以向电解质中添加吡啶、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(hexaphosphorictriamide)、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。如果必要,为了赋予不燃性,电解质可以还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,电解质可以还包含二氧化碳气体、碳酸氟代亚乙酯(FEC)、丙烯磺酸内酯(PRS)、碳酸氟代亚丙酯(FPC)等。
本发明还提供包含所述锂二次电池作为单元电池的电池组。
本发明还提供使用所述电池组作为电源的装置。
特别地,所述装置可以选自:移动电话、便携式计算机、智能电话、智能平板、笔记本电脑、轻型电动车辆(LEV)、电动车辆、混合动力车辆、插电式混合动力车辆和蓄电装置。
结构和制造方法在本领域中是公知的,因此在本说明书中省略了其详细说明。
附图说明
参照附图,由以下的详细说明将会更加清楚地理解本发明的以上和其它目的、特征及其它优点,其中:
图1为根据本发明的一个实施方式的锂二次电池的示意图;且
图2为根据本发明的另一个实施方式的电池壳的示意图。
具体实施方式
现在,将参照附图对本发明进行更详细的说明。这些实施例仅用于说明目的而提供且不应被解释为限制本发明的范围和主旨。
图1示出根据本发明的一个实施方式的锂二次电池的示意图。
参照图1,锂二次电池10包含电极层压体100、电池壳200、气体透过膜300和电解质(未示出)。电池壳200包含空间部210和密封部220,空间部210被内置在电极层压体100中。将气体透过膜300设置在电极层压体100与密封部220之间。因此,可以将从电极层压体100生成的气体排放至气体透过膜300,然后通过密封部220排放至电池的外部。另一方面,由于电解质不可能透过气体透过膜300,所以可以防止电解质的泄露。
图2示出根据本发明另一个实施方式的电池壳的示意图。
参照图2,电池壳20包含第一壳21和第二壳22。第二壳22从第一壳21延伸。
第一壳21和第二壳22由包含内部密封层20A、阻挡层20B和外部涂层20C的层压片构成,层压片具有多个孔20D。由于这种结构,可以将从电极层压体生成的气体通过多个孔20D排放至电池的外部且电解质不可能透过孔,从而防止电解质的泄露。
尽管已经用于说明目的公开了本发明的优选实施方式,但本领域的技术人员将会理解,在不背离如在所附权利要求书中公开的本发明的范围和主旨的情况下,各种修改、添加和替换都是可能的。
[工业实用性]
如上所述,根据本发明的锂二次电池包含气体透过膜,从而当对电池进行活化和使用时,将生成的气体排放至外部、且防止电解质泄露。
Claims (23)
1.一种锂二次电池,其包含:
电解质;
电极层压体;
电池壳,所述电池壳包含其中内置有所述电解质和所述电极层压体的空间部,和包围所述空间部的密封部;以及
气体透过膜。
2.根据权利要求1所述的锂二次电池,其中所述气体透过膜设置在所述空间部中。
3.根据权利要求1所述的锂二次电池,其中所述气体透过膜为液体非透过性的。
4.根据权利要求3所述的锂二次电池,其中所述气体透过膜的孔径为2.0埃~10埃。
5.根据权利要求1所述的锂二次电池,其中所述气体透过膜为选择性地透过氧气(O2)和二氧化碳(CO2)的选择性气体透过膜。
6.根据权利要求5所述的锂二次电池,其中所述选择性气体透过膜的孔径为2.0埃~10埃。
7.根据权利要求1所述的锂二次电池,其中所述气体透过膜由聚对苯二甲酸乙二醇酯(PET)构成。
8.根据权利要求2所述的锂二次电池,其中所述气体透过膜在垂直剖面中设置在所述电极层压体与所述密封部之间。
9.根据权利要求8所述的锂二次电池,其中所述气体透过膜在垂直剖面中分割所述空间部。
10.根据权利要求9所述的锂二次电池,其中所述气体透过膜贯通所述密封部。
11.根据权利要求10所述的锂二次电池,其中所述电池壳包含第一壳和通过结合至所述第一壳而密封所述电池壳的第二壳,且所述气体透过膜置于所述第一壳与所述第二壳之间的界面上。
12.一种电池壳,其包含第一壳和通过结合至所述第一壳而密封所述电池壳的第二壳,其中所述第一壳和所述第二壳由包含内部密封层、阻挡层和外部涂层的层压片构成,并且所述第一壳和所述第二壳中的至少一者全部或部分地由多孔层压片构成。
13.根据权利要求12所述的电池壳,其中所述多孔层压片包含内部多孔密封层、多孔阻挡层和外部多孔涂层,且具有2.0埃~10埃的孔径。
14.根据权利要求12所述的电池壳,其中所述内部密封层由无取向的聚丙烯构成,所述阻挡层由金属构成,且所述外部涂层由聚对苯二甲酸乙二醇酯构成。
15.根据权利要求13所述的电池壳,其中所述内部多孔密封层由无取向的多孔聚丙烯构成,所述多孔阻挡层由多孔金属构成,且所述外部多孔涂层由多孔聚对苯二甲酸乙二醇酯构成。
16.根据权利要求12所述的电池壳,其中所述第二壳从所述第一壳的一部分延伸。
17.根据权利要求12所述的电池壳,其中所述第一壳和所述第二壳为分离的独立构件。
18.一种锂二次电池,其包含:
根据权利要求12所述的电池壳;
电极层压体,其包含至少一个正极、至少一个负极和层压在所述至少一个正极与所述至少一个负极之间的至少一个隔膜;和
电解质。
19.根据权利要求1或18所述的锂二次电池,其包含选自由下式(1)表示的化合物和由下式(2)表示的化合物中的至少一种锂过渡金属氧化物作为正极活性材料:
LixMyMn2-yO4-zAz(1)
其中0.9≤x≤1.2,0<y<2且0≤z<0.2;
M为选自如下的至少一种元素:Al、Mg、Ni、Co、Fe、Cr、V、Ti、Cu、B、Ca、Zn、Zr、Nb、Mo、Sr、Sb、W、Ti和Bi;
A为至少一种一价或二价阴离子,
(1-x)LiM'O2-yAy·xLi2MnO3-y'Ay'(2)
其中M'为MnaMb;
M为选自如下的至少一种:Ni、Ti、Co、Al、Cu、Fe、Mg、B、Cr、Zr、Zn和第Ⅱ周期过渡金属;
A为选自如PO4、BO3、CO3、F和NO3的阴离子中的至少一种;
0<x<1;0<y≤0.02;0<y'≤0.02;0.5≤a≤1.0;0≤b≤0.5;且a+b=1。
20.根据权利要求19所述的锂二次电池,其包含碳系材料和/或Si作为负极活性材料。
21.根据权利要求19所述的锂二次电池,其中所述锂二次电池为锂离子电池、锂离子聚合物电池或锂聚合物电池。
22.一种电池组,其包含根据权利要求1或18所述的锂二次电池。
23.一种装置,其使用根据权利要求22所述的电池组作为能源。
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