CN108102123A - 具有改善的循环特性的电化学装置 - Google Patents
具有改善的循环特性的电化学装置 Download PDFInfo
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- CN108102123A CN108102123A CN201711206402.7A CN201711206402A CN108102123A CN 108102123 A CN108102123 A CN 108102123A CN 201711206402 A CN201711206402 A CN 201711206402A CN 108102123 A CN108102123 A CN 108102123A
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- electrochemical appliance
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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
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
-
- 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
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
- C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
-
- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/52—Removing gases inside the secondary cell, e.g. by absorption
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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Abstract
本发明提供一种电化学装置,包括:(a)复合隔膜,其包括具有孔的多孔基底、涂覆于该多孔基底的一个表面上、由无机颗粒和粘合剂聚合物的混合物形成的第一多孔涂层、和涂覆于所述多孔基底的另一个表面上、由无机颗粒和粘合剂聚合物的混合物形成的第二多孔涂层,其中第一多孔涂层比第二多孔涂层厚;(b)阳极,其朝向第一多孔涂层;和(c)阴极,其朝向第二多孔涂层。本发明的电化学装置兼具良好的热稳定性和改善的循环特性。
Description
本申请是分案申请,其原申请的申请号为201180048005.6,申请日为2011年9月23日,发明名称为“具有改善的循环特性的电化学装置”。
相关申请的互相引用
本申请根据35USC 119(a)要求分别于2010年10月5日和2011年9月21日在韩国提交的第10-2010-0096839和10-2011-0095272号韩国专利申请的优先权,其全部内容以引用的形式纳入本说明书。
技术领域
本发明涉及一种电化学装置,例如锂二次电池,更具体而言,涉及一种包括复合隔膜的电化学装置,在所述复合隔膜中,包括无机颗粒和粘合剂聚合物的混合物的多孔涂层被涂覆于多孔基底上。
背景技术
近来,人们对于能量存储技术越来越感兴趣。随着能量存储技术的应用领域已经拓宽至移动电话、可携式摄像机、笔记本电脑以及甚至电动汽车,人们越来越多地致力于电化学装置的研究和开发。在此方面,电化学装置已引起了极大的关注。能够反复充电和放电的二次电池的开发已成为特别关注的焦点。近年来,为了改善电池的容量密度和比能,已进行广泛的研究和开发来设计新的电极和电池。
目前已存在多种二次电池。在20世纪90年代初期开发的锂二次电池由于其相比于常规的基于水性电解液的电池(例如Ni-MH电池、Ni-Cd电池和H2SO4-Pb电池)具有更高的操作电压和高得多的能量密度的优势,已获得极大的关注。然而,此类锂离子电池由于使用有机电解质而存在安全问题,例如起火或***,且其较复杂而不利于制造。为了克服锂离子电池的缺点,已开发了锂离子聚合物电池作为下一代电池。然而,仍然亟需其它研究来改善锂离子聚合物电池相比于锂离子电池相对低的容量和不足的低温放电容量。
很多公司已经制备出多种具有不同安全特性的电化学装置。确保所述电化学装置的安全性是极其重要的。对安全性的最重要的考量是,电化学装置的操作失误或故障不应对用户造成伤害。为此,安全法规严格限制电化学装置的危险(例如起火和烟雾)的可能性。电化学装置过热可引起热失控或者隔膜的击穿可使得***的风险增加。特别地,通常用作电化学装置隔膜的多孔聚烯烃基底由于其材料特性和制备方法(包括拉伸),在100℃以上的温度下会经历极端的热收缩。这种热收缩行为可引起阴极和阳极之间的短路。
已提出各种方案来解决上述电化学装置的安全性问题。例如,韩国未经审查的第2007-0019958号专利公布公开了一种复合隔膜,其包括多孔基底和涂覆于所述多孔基底的至少一个表面上的多孔涂层,其中该多孔涂层由无机颗粒和粘合剂聚合物的混合物组成。涂覆于所述多孔基底上的多孔涂层中存在的无机颗粒用作间隔剂(spacer),其可保持所述多孔涂层的物理形状从而抑制多孔基底在电化学装置过热时的热收缩。所述无机颗粒之间存在的间隙体积形成所述多孔涂层的细孔。
将复合隔膜***阴极和阳极之间以制备电化学装置。电化学装置的容量随着循环次数的增加趋于相当大的程度地劣化。
发明内容
技术问题
本发明旨在解决现有技术的问题,因此本发明的一个目的是提供一种电化学装置,其中将多孔涂层引入到多孔基底上以实现良好的热稳定性和改善的循环特性。
技术方案
为了实现上述目的,提供一种电化学装置,包括:
(a)复合隔膜,其包括多孔基底、涂覆于该多孔基底的一个表面上并且由包括无机颗粒和粘合剂聚合物的混合物组成的第一多孔涂层、和涂覆于所述多孔基底的另一个表面上并且由包括无机颗粒和粘合剂聚合物的混合物组成的第二多孔涂层,其中所述第一多孔涂层比第二多孔涂层厚;
(b)阳极,其配置成朝向所述第一多孔涂层;和
(c)阴极,其配置成朝向所述第二多孔涂层。
在本发明中,优选所述第一和第二多孔涂层的厚度满足以下关系1:
0.1≤(T1-T2)/Ttot≤0.8 (1)
其中T1和T2分别代表所述第一和第二多孔涂层的厚度,并且Ttot代表所述第一和第二多孔涂层的总厚度。
在本发明中,更优选所述第一和第二多孔涂层的厚度满足以下关系2:
0.2≤(T1-T2)/Ttot≤0.7 (2)
其中T1和T2分别代表所述第一和第二多孔涂层的厚度,并且Ttot代表所述第一和第二多孔涂层的总厚度。
在本发明中,优选所述第一和第二多孔涂层的总厚度为1.0至20.0μm。
在本发明中,优选所述多孔基底为多孔聚烯烃膜并且厚度为1至100μm。
在本发明中,优选所述阴极包括以下物质的颗粒作为阴极活性物质:LiCoO2、LiNiO2、LiMn2O4、LiCoPO4、LiFePO4、LiNiMnCoO2、LiNi1-x-y-zCoxM1yM2zO2(其中M1和M2各自独立地选自Al、Ni、Co、Fe、Mn、V、Cr、Ti、W、Ta、Mg和Mo,并且x、y和z代表所述氧化物的相应组成元素的原子分数并且满足关系式0≤x<0.5,0≤y<0.5,0≤z<0.5)或其混合物。优选所述阳极包括以下物质的颗粒作为阳极活性物质:天然石墨、人造石墨、碳质材料、LTO、硅(Si)、锡(Sn)或其混合物。
有益效果
本发明的电化学装置显示出以下特性。
首先,所述多孔涂层能够在电化学装置过热时抑制多孔基底的热收缩并且在发生热失控时防止两个电极之间短路。
其次,所述复合隔膜的配置(其中将比第二多孔涂层厚的第一多孔涂层设置为朝向阳极)可以降低离子通过阳极表面(在其上副反应比在阴极中发生得更严重)的实际传输速率,从而使得电化学装置的循环特性改善。也就是说,相比于使用包括具有相同厚度的第一多孔涂层和第二多孔涂层的复合隔膜的电化学装置或其中将比第二多孔涂层厚的第一多孔涂层设置为朝向阴极的电化学装置,本发明的电化学装置可防止容量的劣化。
附图说明
本发明的其它目的和方面将由以下实施方案的说明并参照附图而显而易见,其中
图1为示意性地展示本发明的电化学装置中阴极、阳极和复合隔膜构造的分解剖视图。
最佳实施方案
在下文中,参照附图对本发明的优选实施方案进行详细阐述。在阐述之前,应当理解的是,不应将说明书和所附权利要求中使用的术语解释为限于通用含义和字典含义,而应该在允许发明人为了最佳解释可合适地定义术语的原则基础上基于相应于本发明技术方面的含义和概念而理解。
本发明提供了一种电化学装置,包括(a)复合隔膜,其包括多孔基底、涂覆于该多孔基底的一个表面上并且由包括无机颗粒和粘合剂聚合物的混合物组成的第一多孔涂层、和涂覆于所述多孔基底的另一个表面上并且由包括无机颗粒和粘合剂聚合物的混合物组成的第二多孔涂层,其中所述第一多孔涂层比第二多孔涂层厚,(b)阳极,其配置成朝向所述第一多孔涂层,和(c)阴极,其配置成朝向所述第二多孔涂层。
图1是为示意性地说明本发明的一个实施方案的电化学装置中阴极30、阳极20和复合隔膜10的构造的分解剖视图。
参照图1,复合隔膜10包括多孔基底1、涂覆于多孔基底1的一个表面上的第一多孔涂层2、和涂覆于多孔基底1的另一个表面上的第二多孔涂层5。涂覆于多孔基底1的两个表面上的第一多孔涂层2和第二多孔涂层5各自独立地由包括无机颗粒和粘合剂聚合物的混合物组成。多孔涂层2和5中各自存在的无机颗粒作为间隔剂,其可保持多孔涂层2和5的物理形状,从而抑制多孔基底1在电化学装置过热时发生热收缩,或在发生热失控时防止电化学装置的两个电极之间短路。优选使存在于无机颗粒之间的间隙体积形成多孔涂层的细孔。第一多孔涂层2的厚度大于第二多孔涂层5的厚度。
将阳极20和阴极30设置为使其分别朝向复合隔膜10的第一多孔涂层2和第二多孔涂层5。
复合隔膜10的配置——其中将比第二多孔涂层5厚的第一多孔涂层2设置为朝向阳极——可降低离子通过阳极表面(在其上副反应比在阴极中发生得更严重)的实际传输速率,从而使得电化学装置循环特性改善。也就是说,相比较于使用包括具有相同厚度的第一多孔涂层和第二多孔涂层的复合隔膜的电化学装置或其中将比第二多孔涂层厚的第一多孔涂层设置为朝向阴极的电化学装置,本发明的电化学装置可防止容量的劣化。
在本发明的电化学装置中,优选使第一和第二多孔涂层的厚度满足以下关系1:
0.1≤(T1-T2)/Ttot≤0.8 (1)
其中T1和T2分别代表第一和第二多孔涂层的厚度,并且Ttot代表第一和第二多孔涂层的总厚度。第一和第二多孔涂层的总厚度优选为1.0至20.0μm。
更优选使第一和第二多孔涂层的厚度满足以下关系2:
0.2≤(T1-T2)/Ttot≤0.7 (2)
其中T1和T2分别代表第一和第二多孔涂层的厚度,并且Ttot代表第一和第二多孔涂层的总厚度。
在本发明的电化学装置中,多孔基底可为通常用于本领域中的任意多孔基底,其包括各种多孔聚合物膜,例如目前用作电化学装置——特别是锂二次电池——的隔膜的多孔聚烯烃膜,和无纺布,例如由聚邻苯二甲酸乙二醇酯纤维组成的无纺布。多孔基底的材料和形状可根据需要而改变。合适的多孔聚烯烃膜的材料的实例包括:聚乙烯聚合物,例如高密度聚乙烯、线性低密度聚乙烯、低密度聚乙烯和超高分子量聚乙烯;聚丙烯;聚丁烯;以及聚戊烯。这些聚烯烃可单独使用或作为其混合物使用。合适的无纺布的材料的实例包括聚烯烃和具有比聚烯烃更高的耐热性的聚合物。多孔基底的厚度优选为1至100μm,更优选5至50μm,但不特别限于此范围。多孔基底的孔径和孔隙率分别优选为0.001至50μm和10至95%,但不特别限于此范围。多孔基底优选为多孔聚烯烃膜。
在第一和第二多孔涂层中各自包括的无机颗粒没有特别限制,只要其是电化学稳定的即可。换言之,如果无机颗粒在施加于电化学装置的操作电压范围内(例如对于Li/Li+,0-5V)不发生氧化和/或还原,则在本发明中可没有特殊限制地使用所述无机颗粒。具体而言,无机颗粒的高介电常数可有助于增加液体电解质中盐(例如锂盐)的解离度,从而改善电解质的离子电导率。
基于这些理由,优选所述无机颗粒具有至少为5、优选至少为10的高介电常数。具有至少为5的介电常数的无机颗粒的非限制性实例包括BaTiO3、Pb(Zr,Ti)O3(PZT)、Pb1- xLaxZr1-yTiyO3(PLZT,0<x<1,0<y<1)、Pb(Mg1/3Nb2/3)O3-PbTiO3(PMN-PT)、二氧化铪(HfO2)、SrTiO3、SnO2、CeO2、MgO、NiO、CaO、ZnO、ZrO2、Y2O3、Al2O3、TiO2和SiC颗粒。这些无机颗粒可单独使用或作为其混合物使用。
所述无机颗粒可为具有传输锂离子能力的那些,即包含锂原子并具有传递锂离子而不存储锂的功能的那些。具有传输锂离子能力的无机颗粒的非限制性实例包括磷酸锂(Li3PO4)颗粒、磷酸钛锂(LixTiy(PO4)3,0<x<2,0<y<3)颗粒、磷酸钛铝锂(LixAlyTiz(PO4)3,0<x<2,0<y<1,0<z<3)颗粒、(LiAlTiP)xOy型玻璃(0<x<4,0<y<13)颗粒(例如14Li2O-9Al2O3-38TiO2-39P2O5颗粒)、酞酸镧锂(LixLayTiO3,0<x<2,0<y<3)颗粒、硫代磷酸锗锂(LixGeyPzSw,0<x<4,0<y<1,0<z<1,0<w<5)颗粒(例如Li3.25Ge0.25P0.75S4颗粒)、氮化锂(LixNy,0<x<4,0<y<2)颗粒(例如Li3N颗粒)、SiS2型玻璃(LixSiySz,0<x<3,0<y<2,0<z<4)颗粒(例如Li3PO4-Li2S-SiS2颗粒)、和P2S5型玻璃(LixPySz,0<x<3,0<y<3,0<z<7)颗粒(例如LiI-Li2S-P2S5颗粒)。这些无机颗粒可单独使用或作为其混合物使用。
所述无机颗粒的平均粒径不受限制但优选在0.001至10μm的范围内。此范围确保涂层具有均一的厚度及最佳的孔隙率。平均粒径低于0.001μm可导致分散性劣化。同时,平均粒径超过10μm会增加涂层的厚度。
在第一和第二多孔涂层中各自包括的粘合剂聚合物优选具有的玻璃化转变温度(Tg)在–200℃至200℃范围内。在此范围内,可改善涂层的机械性能(例如,柔性和弹性)。
所述粘合剂聚合物并不一定需要具有传导离子的能力。然而,由于粘合剂聚合物的离子电导率可进一步改善电化学装置的性能,因此优选粘合剂聚合物具有尽可能高的介电常数。实际上,电解质中盐的解离度取决于电解质中溶剂的介电常数。因此,更高的粘合剂聚合物介电常数可使得电解质中盐的解离度更高。粘合剂聚合物的介电常数在1.0至100范围内(在1kHz频率下测量),特别优选10以上。
此外,用液体电解质浸渍粘合剂聚合物可使粘合剂聚合物胶凝化,导致粘合剂聚合物高度溶胀。为了高度溶胀,粘合剂聚合物优选具有的溶度参数为15至45Mpa1/2,更优选15至25Mpa1/2以及30至45Mpa1/2。因此,具有多个极性基团的亲水性聚合物比疏水性聚合物(例如聚烯烃)更优选作为粘合剂聚合物。溶度参数低于15Mpa1/2或超过45Mpa1/2使得粘合剂聚合物难以在通常用于电池的液体电介质中溶胀。
所述粘合剂聚合物的非限制性实例包括聚偏二氟乙烯-共-六氟丙烯、聚偏二氟乙烯-共-三氯乙烯、聚甲基丙烯酸甲酯、聚丙烯酸丁酯、聚丙烯腈、聚乙烯基吡咯烷酮、聚乙酸乙烯酯、聚乙烯-共-乙酸乙烯酯、聚环氧乙烷、聚丙烯酸酯、乙酸纤维素、乙酸丁酸纤维素、乙酸丙酸纤维素、氰基乙基普鲁兰多糖(cyanoethylpullulan)、氰基乙基聚乙烯醇、氰基乙基纤维素、氰基乙基蔗糖、普鲁兰多糖,以及羧甲基纤维素。这些粘合剂聚合物可单独使用或作为其两种以上的混合物使用。
在第一和第二多孔涂层中各自包括的无机颗粒和粘合剂聚合物的重量比优选在50:50至99:1、更优选70:30至95:5的范围内。如果无机颗粒以低于50重量%的含量存在(即,粘合剂聚合物以相对大的含量存在),则多孔涂层的孔径和孔隙率会降低。同时,如果无机颗粒以超过99重量%的含量存在(即,粘合剂聚合物以极小含量存在),则多孔涂层的抗剥离性能会劣化。
在本发明的电化学装置中,阴极和阳极可以是本领域已知的那些。通常可通过以下方法制备阴极和阳极:制备包含相应的电极活性物质颗粒的浆料,将所述浆料施用于相应的集流体,并干燥所述浆料。优选的用于阴极的阴极活性物质的实例包括,但不限于,LiCoO2、LiNiO2、LiMn2O4、LiCoPO4、LiFePO4、LiNiMnCoO2和LiNi1-x-y-zCoxM1yM2zO2(其中M1和M2各自独立地选自Al、Ni、Co、Fe、Mn、V、Cr、Ti、W、Ta、Mg和Mo,并且x、y和z代表所述氧化物的相应组成元素的原子分数并满足关系0≤x<0.5,0≤y<0.5,0≤z<0.5)。这些阴极活性物质可单独使用或作为其两种以上的混合物使用。阴极中特别优选包括LiCoO2和LiNiMnCoO2中的至少一种。
优选的用于阳极的阳极活性物质的实例包括,但不限于,天然石墨、人造石墨、碳质材料、LTO、硅(Si)和锡(Sn)。这些阳极活性物质可单独使用或作为其两种以上的混合物使用。
对用于制备本发明电化学装置的方法没有限制。例如,电化学装置可通过以下步骤制备。
首先,将粘合剂聚合物溶解在溶剂中以制备溶液,再将有机颗粒添加并分散于所述溶液中以制备浆料。所述溶剂优选具有类似于粘合剂聚合物的溶度参数并具有低沸点,这有利于均匀混合并易于除去溶剂。可用于溶解粘合剂聚合物的溶剂的非限制性实例包括丙酮、四氢呋喃、二氯甲烷、氯仿、二甲基甲酰胺、N-甲基-2-吡咯烷酮(NMP)、环己烷以及水。这些溶剂可单独使用或作为其混合物使用。优选在加入到聚合物溶液后粉碎无机颗粒。同时,粉碎适当地进行1至20小时。优选将无机颗粒粉碎至粒度为0.001至10μm。所述无机颗粒可通过本领域已知的任何适当技术进行粉碎。特别优选球磨。
随后,将所述浆料在10至80%的湿度下涂覆于多孔基底的两个表面上,之后进行干燥以形成具有不同厚度的多孔涂层。将具有较大厚度的多孔涂层定义为第一多孔涂层,并将具有较小厚度的多孔涂层定义为第二多孔涂层。
所述浆料可通过本领域已知的适当技术涂覆在多孔基底上,例如模涂法、辊涂法和浸涂法。多孔涂层的厚度可例如通过以下方法控制:将多孔基底浸渍于浆料中以用浆料对多孔基底的两个表面进行涂覆并且使用具有不同线尺寸的Mayer棒调节涂层至不同厚度。
将由此制备的复合隔膜***阴极和阳极之间。具体而言,以这样的方式配置复合隔膜:使第一多孔涂层和第二多孔涂层分别设置成朝向阳极和阴极。复合隔膜和电极的构造没有特别限制,只要复合隔膜与两个电极存在物理接触即可。如果需要,可将复合隔膜和电极互相层压。
本发明的电化学装置包括所有其中发生电化学反应的装置。所述电化学装置的具体实例包括所有种类的原电极、二次电池、燃料电池、太阳能电池和电容器,例如超级电容器。特别优选锂二次电池,包括锂金属二次电池、锂离子二次电池、锂聚合物二次电池和锂离子聚合物二次电池。
本发明的电化学装置可通过本领域已知的适当方法制备。例如,所述电化学装置可通过将由阴极、阳极和复合隔膜组成的电极结构密封在一个外壳(例如袋子)中,并将电解质注入该电极结构中而制备。
本发明的电解质电化学装置可使用由盐和能够溶解或解离所述盐的有机溶剂组成的电解质。所述盐具有由A+B-代表的结构,其中A+是碱金属阳离子,例如Li+、Na+、K+或其结合,并且B-是阴离子,例如PF6 -、BF4 -、Cl-、Br-、I-、ClO4 -、AsF6 -、CH3CO2 -、CF3SO3 -、N(CF3SO2)2 -、C(CF2SO2)3 -或其结合。适用于溶解或解离所述盐的有机溶剂的实例包括,但不限于,碳酸异丙烯酯(PC)、碳酸亚乙酯(EC)、碳酸二乙酯(DEC)、碳酸二甲酯(DMC)、碳酸二丙酯(DPC)、二甲基亚砜、乙腈、二甲氧基乙烷、二乙氧基乙烷、四氢呋喃、N-甲基-2-吡咯烷酮(NMP)、碳酸乙基甲酯(EMC)和γ-丁内酯。这些有机溶剂可单独使用或作为其混合物使用。
根据制造方法和所需的最终产品的物理特性,电解质可在电化学装置制备期间的任意合适步骤中注入。具体而言,电解质可在电池组装前注入或在电池组装的最后一步中注入。
本发明的实施方案
下文将对本发明实施方案进行具体阐述。然而,本发明的实施方案可采取多种其它形式,并且本发明范围不应被理解为限于以下实施例。提供本发明的实施方案是为了向本发明所属领域的技术人员更全面地解释本发明。
实施例
实施例1
制备复合隔膜
在50℃下将聚偏二氟乙烯-共-三氟氯乙烯(PVdF-CTFE)和氰基乙基普鲁兰多糖以10:2的重量比添加并溶解于丙酮中至少约12小时。将重量比为9:1的Al2O3粉末和BaTiO3粉末的混合物添加到所述聚合物溶液中使得聚合物和无机颗粒的重量比为10:90。将无机颗粒通过球磨粉碎12小时并分散于所述溶液中以制备浆料。该浆料的无机颗粒经测量具有600nm的平均粒径。
将9μm厚的多孔聚乙烯膜(ND209,Asahi)浸渍于所述浆料中以用浆料对其两个表面进行涂覆。使用线尺寸为0.5mm和0.7mm的两个Mayer棒控制所述涂层的厚度。通过干燥除去溶剂以形成厚度为4.2μm(第一多孔涂层)和2.6μm(第二多孔涂层)的两个多孔涂层。第一涂层(T1)和第二涂层(T2)之间的厚度差除以两个涂层的总厚度(Ttot)。计算值(T1-T2)/Ttot为约0.24。
制作电池
将复合隔膜***阴极(涂覆有作为阴极活性物质颗粒的LiCoO2颗粒)和阳极(由涂覆有作为阳极活性物质颗粒的石墨颗粒(涂覆于铜薄膜上)的铜(Cu)薄膜组成)之间。以这样的方式配置复合隔膜:使第一多孔涂层和第二多孔涂层分别设置成朝向阳极和阴极。卷绕并组装所述电极结构。
将溶于碳酸亚乙酯(EC)和碳酸乙基甲酯(EMC)的混合有机溶剂(1/2,w/w)中的六氟磷酸锂(LiPF6,1摩尔)的非水性电解质注入电极组件中以制作锂二次电池。
实施例2
重复实施例1的步骤,除了通过狭缝涂布形成厚度为5.3μm的第一多孔涂层并且通过辊涂法形成厚度为1.5μm的第二多孔涂层之外。即,(T1-T2)/Ttot的值为约0.56。
实施例3
重复实施例1的步骤,除了通过狭缝涂布形成厚度为3.9μm的第一多孔涂层并且通过辊涂法形成厚度为3.1μm的第二多孔涂层之外。即,(T1-T2)/Ttot的值为约0.11。
实施例4
重复实施例1的步骤,除了使用Li(NiMnCo)O2颗粒作为阴极活性物质颗粒之外。
对比实施例1
以与实施例1中相同方式制作锂二次电池,除了使用厚度为0.6mm的两个Mayer棒将涂覆于多孔膜的两个表面的涂层厚度调节至相同水平(3.4μm)之外。
对比实施例2
以与实施例1中相同方式制作锂二次电池,除了以这样的方式配置复合隔膜:使2.6μm厚的第二多孔涂层设置成朝向阳极(由涂覆有作为阳极活性物质颗粒的石墨颗粒(涂覆在铜薄膜上)的铜(Cu)薄膜组成)并且4.2μm厚的第一多孔涂层设置成朝向阴极(涂覆有作为阴极活性物质颗粒的LiCoO2颗粒)之外。
对比实施例3
重复对比实施例1的步骤,除了使用Li(NiMnCo)O2颗粒作为阴极活性物质颗粒之外。
电池容量评估
测量实施例1-4和对比实施例1-3中所制作的电池的循环特性。结果示于表1和2中。
表1
表2
由表1和表2中的结果可看出,与对比实施例1的电池(其中形成了具有相同厚度的第一和第二多孔涂层)以及对比实施例2的电池(其中比第二多孔涂层厚的第一多孔涂层设置成朝向阴极)相比,实施例1-3的电池(其中比第二多孔涂层厚的第一多孔涂层设置成朝向阳极)显示出改善的循环特性。当将使用不同种类的阴极活性物质的实施例4和对比实施例3的电池进行比较时,前者在循环特性上优于后者。
Claims (14)
1.一种电化学装置,包括:
(a)复合隔膜,其包括多孔基底、涂覆于该多孔基底的一个表面上并且由包括无机颗粒和粘合剂聚合物的混合物组成的第一多孔涂层、和涂覆于所述多孔基底的另一个表面上并且由包括无机颗粒和粘合剂聚合物的混合物组成的第二多孔涂层,其中第一多孔涂层比第二多孔涂层厚;
(b)阳极,其设置成朝向第一多孔涂层;和
(c)阴极,其设置成朝向第二多孔涂层。
2.权利要求1的电化学装置,其中第一和第二多孔涂层的厚度满足以下关系1:
0.1≤(T1-T2)/Ttot≤0.8 (1)
其中T1和T2分别代表第一和第二多孔涂层的厚度,并且Ttot代表第一和第二多孔涂层的总厚度。
3.权利要求2的电化学装置,其中第一和第二多孔涂层的厚度满足以下关系2:
0.2≤(T1-T2)/Ttot≤0.7 (2)
其中T1和T2分别代表第一和第二多孔涂层的厚度,并且Ttot代表第一和第二多孔涂层的总厚度。
4.权利要求2的电化学装置,其中第一和第二多孔涂层的总厚度为1.0至20.0μm。
5.权利要求1的电化学装置,其中多孔基底是多孔聚烯烃膜。
6.权利要求1的电化学装置,其中多孔基底的厚度为1至100μm。
7.权利要求1的电化学装置,其中粘合剂聚合物各自独立地具有15至45Mpa1/2的溶度参数。
8.权利要求1的电化学装置,其中粘合剂聚合物各自独立地选自聚偏二氟乙烯-共-六氟丙烯、聚偏二氟乙烯-共-三氯乙烯、聚甲基丙烯酸甲酯、聚丙烯酸丁酯、聚丙烯腈、聚乙烯基吡咯烷酮、聚乙酸乙烯酯、聚乙烯-共-乙酸乙烯酯、聚环氧乙烷、聚丙烯酸酯、乙酸纤维素、乙酸丁酸纤维素、乙酸丙酸纤维素、氰基乙基普鲁兰多糖、氰基乙基聚乙烯醇、氰基乙基纤维素、氰基乙基蔗糖、普鲁兰多糖、羧甲基纤维素,及其两种以上的混合物。
9.权利要求1的电化学装置,其中第一和第二多孔涂层中各自存在的无机颗粒的平均粒径为0.001至10μm。
10.权利要求1的电化学装置,其中第一和第二多孔涂层各自的无机颗粒与粘合剂聚合物的重量比为50:50至99:1。
11.权利要求1的电化学装置,其中阴极包括至少一种选自LiCoO2、LiNiO2、LiMn2O4、LiCoPO4、LiFePO4、LiNiMnCoO2和LiNi1-x-y-zCoxM1yM2zO2(其中M1和M2各自独立地选自Al、Ni、Co、Fe、Mn、V、Cr、Ti、W、Ta、Mg和Mo,并且x、y和z代表所述氧化物相应组成元素的原子分数并且满足关系0≤x<0.5,0≤y<0.5,0≤z<0.5)的阴极活性物质的颗粒。
12.权利要求1的电化学装置,其中阴极包括至少一种选自LiCoO2和LiNiMnCoO2的阴极活性物质。
13.权利要求1的电化学装置,其中阳极包括至少一种选自天然石墨、人造石墨、碳质材料、LTO、硅(Si)和锡(Sn)的阳极活性物质的颗粒。
14.权利要求1的电化学装置,其中电化学装置是锂二次电池。
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EP2626942A2 (en) | 2013-08-14 |
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US9368777B2 (en) | 2016-06-14 |
KR101625592B1 (ko) | 2016-05-30 |
KR20140014304A (ko) | 2014-02-05 |
WO2012046966A2 (ko) | 2012-04-12 |
EP2626942B1 (en) | 2016-07-13 |
WO2012046966A3 (ko) | 2012-06-07 |
CN103155258A (zh) | 2013-06-12 |
JP5902692B2 (ja) | 2016-04-13 |
US8778524B2 (en) | 2014-07-15 |
US20120251869A1 (en) | 2012-10-04 |
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