CN106207249A - 锂离子二次电池 - Google Patents
锂离子二次电池 Download PDFInfo
- Publication number
- CN106207249A CN106207249A CN201610319877.6A CN201610319877A CN106207249A CN 106207249 A CN106207249 A CN 106207249A CN 201610319877 A CN201610319877 A CN 201610319877A CN 106207249 A CN106207249 A CN 106207249A
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- packaging body
- modified polypropene
- Prior art date
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 49
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 239000004743 Polypropylene Substances 0.000 claims abstract description 124
- 229920001155 polypropylene Polymers 0.000 claims abstract description 123
- -1 polypropylene Polymers 0.000 claims abstract description 74
- 238000004806 packaging method and process Methods 0.000 claims abstract description 69
- 239000002253 acid Substances 0.000 claims abstract description 49
- 229910052751 metal Inorganic materials 0.000 claims abstract description 25
- 239000002184 metal Substances 0.000 claims abstract description 25
- 230000004888 barrier function Effects 0.000 claims abstract description 16
- 239000003792 electrolyte Substances 0.000 claims abstract description 16
- 238000003466 welding Methods 0.000 claims description 12
- 239000012943 hotmelt Substances 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 23
- 239000007774 positive electrode material Substances 0.000 description 19
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- 239000000463 material Substances 0.000 description 15
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- 150000001336 alkenes Chemical class 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 8
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- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
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- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 5
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- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 description 1
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical class C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- DZAHXNNEQCZPGJ-UHFFFAOYSA-N CCCCOC(OC)=O.COC(O)=O Chemical compound CCCCOC(OC)=O.COC(O)=O DZAHXNNEQCZPGJ-UHFFFAOYSA-N 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- ZDQWESQEGGJUCH-UHFFFAOYSA-N Diisopropyl adipate Chemical compound CC(C)OC(=O)CCCCC(=O)OC(C)C ZDQWESQEGGJUCH-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
- 229910003005 LiNiO2 Inorganic materials 0.000 description 1
- 229910014174 LixNiy Inorganic materials 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 240000001439 Opuntia Species 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
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- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical class [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 description 1
- SOXUFMZTHZXOGC-UHFFFAOYSA-N [Li].[Mn].[Co].[Ni] Chemical compound [Li].[Mn].[Co].[Ni] SOXUFMZTHZXOGC-UHFFFAOYSA-N 0.000 description 1
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- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
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- 230000015572 biosynthetic process Effects 0.000 description 1
- UXXXZMDJQLPQPH-UHFFFAOYSA-N bis(2-methylpropyl) carbonate Chemical compound CC(C)COC(=O)OCC(C)C UXXXZMDJQLPQPH-UHFFFAOYSA-N 0.000 description 1
- JKJWYKGYGWOAHT-UHFFFAOYSA-N bis(prop-2-enyl) carbonate Chemical compound C=CCOC(=O)OCC=C JKJWYKGYGWOAHT-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- CKFRRHLHAJZIIN-UHFFFAOYSA-N cobalt lithium Chemical compound [Li].[Co] CKFRRHLHAJZIIN-UHFFFAOYSA-N 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
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- 150000005676 cyclic carbonates Chemical class 0.000 description 1
- QLVWOKQMDLQXNN-UHFFFAOYSA-N dibutyl carbonate Chemical compound CCCCOC(=O)OCCCC QLVWOKQMDLQXNN-UHFFFAOYSA-N 0.000 description 1
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- 150000002500 ions Chemical class 0.000 description 1
- 150000002641 lithium Chemical class 0.000 description 1
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
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- 238000004519 manufacturing process Methods 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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- PFPYHYZFFJJQFD-UHFFFAOYSA-N oxalic anhydride Chemical compound O=C1OC1=O PFPYHYZFFJJQFD-UHFFFAOYSA-N 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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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
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- H—ELECTRICITY
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- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- H—ELECTRICITY
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- H01M50/102—Primary casings; Jackets or wrappings characterised by their shape or physical structure
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- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/131—Primary casings; Jackets or wrappings characterised by physical properties, e.g. gas permeability, size or heat resistance
- H01M50/133—Thickness
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
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- B32B15/085—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyolefins
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
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Abstract
本发明提供一种锂离子二次电池。所述锂离子二次电池包括封装体,在所述封装体的内部收纳有正极、负极、隔膜和电解液,所述封装体包括层叠体,所述层叠体包括依次层叠的金属基材、酸改性聚丙烯层以及聚丙烯层,所述聚丙烯层形成所述封装体的内表面,所述封装体具有热熔接部和非熔接部,所述热熔接部所包括的1层的所述酸改性聚丙烯层的厚度的值,小于所述热熔接部所包括的所述聚丙烯层的厚度的值的二分之一。
Description
相关申请的交叉参考
本申请要求2015年06月01日向日本特许厅提交的日本专利申请第2015-111692号的优先权,因此将所述日本专利申请的全部内容以引用的方式并入本文。
技术领域
本发明涉及锂离子二次电池。
背景技术
非水电解质电池作为包括混合动力汽车和电动汽车等汽车用的电池已经实用化了。作为这种车载电源用电池,使用锂离子二次电池。对应于对车载电源用电池的薄型化和轻量化的要求,提供有片状的锂离子二次电池。该锂离子二次电池具有由包括金属基材的层叠膜形成的封装体。在该封装体内部收纳有包括正极、负极和隔膜的发电元件以及电解液。
提出有下述的一种技术方案:作为形成电池的封装体的层叠膜,使用层叠体,所述层叠体包括从封装体的外侧朝向内侧依次层叠的双轴拉伸尼龙膜层、金属箔层、粘合性强化层和热粘合性树脂层(日本专利公开公报特开2011-142092号)。在此,粘合性强化层例如由酸改性丙烯系共聚物等形成。此外,热粘合性树脂层例如由丙烯-乙烯共聚物、丙烯-乙烯-α-烯烃共聚物、或丙烯-乙烯-丁烯三元共聚物形成。
当将这种层叠膜作为电池的封装体使用时,例如通过以用2个层叠膜夹着电池的构成元件(正极、负极和隔膜等)的方式将所述层叠膜的外周彼此热熔接来形成封装体。在该封装体内部收纳非水电解液后,密封该封装体。此后,封装体内侧的热粘合性树脂层与非水电解液接触。由有机聚合物形成的热粘合性树脂层,逐渐被作为有机物质的非水电解液渗透。所述非水电解液通过热粘合性树脂层后能到达粘合性强化层和金属箔层。此时,相比于由非极性聚合物形成的热粘合性树脂层,由具有极性基团的聚合物形成的粘合性强化层一方更容易被非水电解液透过。因此,存在非水电解液顺着粘合性强化层漏出到封装体外部的问题。
发明内容
本发明的目的在于提供一种锂离子二次电池,其通过防止非水电解液向电池外部泄漏来防止电池的电解液缺乏,并由此具有延长了的电池寿命。
本发明的实施方式的锂离子二次电池,其包括封装体,在所述封装体的内部收纳有正极、负极、隔膜和电解液,所述封装体包括层叠体,所述层叠体包括依次层叠的金属基材、酸改性聚丙烯层以及聚丙烯层,所述聚丙烯层形成所述封装体的内表面,所述封装体具有热熔接部和非熔接部,所述热熔接部所包括的1层的所述酸改性聚丙烯层的厚度的值,小于所述热熔接部所包括的所述聚丙烯层的厚度的值的二分之一。
本发明的实施方式的锂离子二次电池,其具有封装体,所述封装体在内部包括发电元件和电解液,所述发电元件包括正极、负极和隔膜。此外,封装体包括层叠体,所述层叠体包括依次层叠的金属基材、酸改性聚丙烯层和聚丙烯层。此时,封装体的热熔接部的酸改性聚丙烯层的1层的厚度,小于聚丙烯层的厚度的二分之一。
按照本发明的锂离子二次电池,通过抑制电解液的泄漏,能够防止电解液缺乏。因此,电池寿命能够延长。
附图说明
图1是表示本发明的一个实施方式的锂离子二次电池的剖视示意图。
图2A和图2B是封装体的热熔接部和非熔接部的放大图。
具体实施方式
在下面的详细说明中,出于说明的目的,为了提供对所公开的实施方式的彻底的理解,提出了许多具体的细节。然而,显然可以在没有这些具体细节的前提下实施一个或更多的实施方式。在其它的情况下,为了简化制图,示意性地示出了公知的结构和装置。
以下说明本发明的实施方式。在本实施方式中,正极是薄板状或者片状的电池部件,该部件具有正极活性物质层,所述正极活性物质层是通过在金属箔等正极集电体上涂布或滚压(rolling)包含正极活性物质、粘合剂和必要时的导电助剂的混合物后经过干燥工序而形成的。负极是薄板状或者片状的电池部件,该部件具有负极活性物质层,所述负极活性物质层是通过在负极集电体上涂布包含负极活性物质、粘合剂和必要时的导电助剂的混合物而形成的。隔膜是膜状的电池部件,该部件通过将正极和负极隔离,确保负极和正极之间的锂离子的传导性。电解液是通过将离子性物质溶解在溶剂中得到的导电性溶液。在本实施方式中,尤其可以采用非水电解液。包括正极、负极和隔膜的发电元件,是电池的主构成部件的一个单位。通常,所述发电元件是包括隔着隔膜重叠(层叠)的正极和负极的层叠体。在本发明的实施方式的锂离子二次电池中,所述层叠体浸渍在电解液中。
本实施方式的锂离子二次电池包括封装体以及收纳在该封装体内部的所述发电元件。优选的是,发电元件收纳在密封了的封装体内部。在此,“密封”的意思是指发电元件以不接触外部空气的方式被后述的封装体材料包裹。即,封装体具有能够在其内部收纳发电元件且能被密封的袋状。
参照附图说明本实施方式的锂离子二次电池的构成例子。图1表示了锂离子二次电池的剖视图的一个例子。锂离子二次电池10包括负极集电体11、负极活性物质层13、隔膜17、正极集电体12和正极活性物质层15作为主要构成部件。在图1中,在负极集电体11的两面设有负极活性物质层13。在正极集电体12的两面设有正极活性物质层15。但是,也可以仅在各集电体的单面上形成活性物质层。负极集电体11、正极集电体12、负极活性物质层13、正极活性物质层15和隔膜17是一个电池的构成单位亦即发电元件(图中的单电池19)。多个这样的单电池19通过隔膜17层叠。从各负极集电体11延伸的延伸部,统一连接在负极引线25上。从各正极集电体12延伸的延伸部,统一连接在正极引线27上。另外,作为正极引线优选使用铝板,作为负极引线优选使用铜板。根据需要,铝板和铜板也可以具有由其它金属(例如镍、锡或者焊锡)或高分子材料形成的局部覆盖层。正极引线和负极引线分别焊接在正极和负极上。通过封装体29以将被焊接了的负极引线25和正极引线27向外部引出的方式封装包括多个层叠的单电池的电池。向封装体29的内部注入电解液31。封装体29具有通过对2个重叠的层叠体的周缘部进行热熔接而得到的形状。
封装体具有层叠体,所述层叠体包括依次层叠的金属基材、酸改性聚丙烯层和聚丙烯层。在层叠体的金属基材的表面,也可以进一步形成尼龙层或者聚对苯二甲酸乙二醇酯层等聚合物覆盖层。封装体以使该层叠体的聚丙烯层形成封装体的内表面的方式形成。
构成层叠体的金属基材是适合作为电池的封装膜使用的基材,优选的是金属箔。作为使用的金属基材的例子,可以举出铝、镍、铁、铜、不锈钢和锡的箔。金属基材具有将在内部收纳了非水电解液的封装体密封的功能。
形成酸改性聚丙烯层的“酸改性聚丙烯”的意思是指包含通过接枝反应导入的酸的聚丙烯。但是,在本实施方式中,通过将酸导入丙烯-乙烯共聚物、丙烯-乙烯-丁烯共聚物或者聚丙烯-丁烯共聚物等作为共聚成分导入了丙烯的共聚物而得到的共聚物,也包含在“酸改性聚丙烯”中。作为通过接枝反应导入的酸的例子,可以举出丙烯酸、甲基丙烯酸、马来酸、马来酸酐、衣康酸和衣康酸酐。通过导入马来酸酐得到的马来酸酐改性聚丙烯、马来酸酐改性丙烯-乙烯共聚物、马来酸酐改性丙烯-乙烯-丁烯共聚物和马来酸酐改性聚丙烯-丁烯共聚物,是代表性的“酸改性聚丙烯”。酸改性聚丙烯具有将金属基材和后述的聚丙烯层粘合的功能。
在形成本实施方式中所使用的聚丙烯层的“聚丙烯”的例子中,除了丙烯的均聚物以外,还包括丙烯-乙烯共聚物、丙烯-乙烯-丁烯共聚物、聚丙烯-丁烯共聚物、丙烯-4-甲基戊烯-1共聚物和丙烯-己烯共聚物等丙烯和其它烯烃的共聚物的全部。所述“聚丙烯”也可以是所述的物质的混合物。聚丙烯层发挥赋予层叠体柔软性的作用。
层叠体的各层的厚度,可以根据该层叠体作为封装体使用的锂离子二次电池的尺寸和形状改变。例如,金属基材的厚度可以设定为15~90μm的范围,优选的是设定为25~60μm的范围。酸改性聚丙烯层的厚度可以设定为10~60μm的范围,优选的是设定为10~40μm的范围。聚丙烯层的厚度可以设定为30~80μm的范围,优选的是设定为40~70μm的范围。其中,可以调整酸改性聚丙烯层的厚度与聚丙烯层的厚度之比。酸改性聚丙烯层的厚度与聚丙烯层的厚度之比,优选的是在1:7~1:2的范围内。优选的是,酸改性聚丙烯层的厚度小于聚丙烯层的厚度。
在此,参照图2A和图2B。图2A是本实施方式的锂离子二次电池的热熔接部周边的放大图。可以通过将重叠的、具有适当大小的层叠体291和层叠体292的周围热熔接来形成本实施方式中使用的封装体29。层叠体291包括层叠的覆盖层41、金属基材51、酸改性聚丙烯层61和聚丙烯层71。同样地,层叠体292包括层叠的覆盖层42、金属基材52、酸改性聚丙烯层62和聚丙烯层72。通过将层叠体291的聚丙烯层71与层叠体292的聚丙烯层72合在一起并进行热熔接来形成封装体29。即,封装体29具有通过将层叠体彼此热熔接形成的热熔接部100以及未熔接的非熔接部200。热熔接部100所包括的一方的层叠体291的聚丙烯层71与另一方的层叠体292的聚丙烯层72彼此融合成为一体。在此,热熔接部100所包括的酸改性聚丙烯层61和酸改性聚丙烯层62各自的厚度,可以小于热熔接部100所包括的一体化了的聚丙烯层的厚度的二分之一。在此,各层的厚度的意思是指热熔接部100所包括的各层整体的厚度的平均值。热熔接部100以包围封装体29的内部的方式形成在将封装体29的周缘部。热熔接部100的宽度设定为约1.0~20.0mm的范围,优选的是设定为2.0~10.0mm的范围,更优选的是设定为3.0~5.0mm的范围。“热熔接部所包括的酸改性聚丙烯层的厚度”的意思是指具有所述宽度的热熔接部100所包括的酸改性聚丙烯层整体的厚度的平均值。即,在图2中,由a表示的1层酸改性聚丙烯层61的厚度以及由b表示的一体化了的聚丙烯层的厚度,表示热熔接部100所包括的各层整体的厚度的平均值。其结果,“热熔接部100所包括的酸改性聚丙烯层61和酸改性聚丙烯层62各自的厚度的值小于热熔接部100所包括的一体化了的聚丙烯层的厚度值的二分之一”的意思是指满足a<(1/2)b的关系。
优选的是,所述一体化了的聚丙烯层的厚度的值的二分之一与所述1层酸改性聚丙烯层的厚度的值之比为2以上。即,在图2A中,(1/2)b与a之比为2以上。换句话说,优选的是,满足(1/2)b≧2a的关系。如果两层的厚度之比满足这样的关系,则容易透过非水电解液的酸改性聚丙烯层变得比聚丙烯层充分薄。因此,能够防止因非水电解液渗透酸改性聚丙烯层而导致的电解液向封装体外的漏出。
此外,在形成封装体的热熔接部时,存在因层叠膜的按压而使热粘合性树脂层产生变扁等变形的情况。在该情况下,非水电解液在早期阶段就会到达粘合性强化层。由此,非水电解液会很快漏出到封装体外部。在这种结构下,估计非水电解液漏出到封装体外部至少会花费十年左右的时间。可是,考虑与汽车的寿命的平衡,将这种电池用作车载电源用电池时,存在问题。因此,如果考虑车辆的寿命,本实施方式的锂离子二次电池作为汽车用电池用尤其有用。
参照图2A说明本实施方式的锂离子二次电池的其它实施方式。优选的是,封装体的热熔接部所包括的1层酸改性聚丙烯层的厚度的值和所述一体化了的聚丙烯层的厚度的值的二分之一的和、与封装体的非熔接部所包括的1层酸改性聚丙烯层的厚度的值和所述非熔接部所包括的1层聚丙烯层的厚度的值的和之比,处于50~95%的范围。即,图2A所示的[a]和[(1/2)b]的和[a+(1/2)b]、与非熔接部200所包括的1层酸改性聚丙烯层61(或酸改性聚丙烯层62)的厚度的值[A]和非熔接部200所包括的1层聚丙烯层71(或聚丙烯层72)的厚度的值[B]的和[A+B]之比,处于50~95%的范围。
通过边对重叠的层叠体291和层叠体292施加热量边进行按压(热封)来形成热熔接部100。该部分的层叠体由于变形,比非熔接部200这部分的层叠体稍稍变扁。该变扁的程度,优选的是处于50~95%的范围。如果所述比小于50%,则在热熔接部,作为绝缘材料的酸改性聚丙烯层和聚丙烯层变薄。其结果,电解液到金属基材为止的到达距离变短。因此,电池的绝缘性降低。此外,如果所述比超过95%,则由于酸改性聚丙烯层和聚丙烯层较厚,因此存在热熔接部未适当地被熔接的可能性。另外,如图2B所示,在热熔接部100所包括的聚丙烯层71和聚丙烯层72的变扁的程度大的情况下,层叠体291的聚丙烯层71和层叠体292的聚丙烯层72大幅变形。其结果,存在一体化了的聚丙烯层的一部分伸出到封装体29的内部的情况。由此,在热熔接部100和非熔接部200之间产生边界部300的情况下,在本实施方式中,在计算所述的层的厚度的平均值时不考虑所述边界部300所包括的各层的厚度。
说明本实施方式的锂离子二次电池的其它实施方式(未图示)。优选的是,所述封装体的所述热熔接部所包括的1层所述酸改性聚丙烯层的厚度的值和所述一体化了的聚丙烯层的厚度的值的和、与封装体的非熔接部所包括的1层酸改性聚丙烯层的厚度的值和所述非熔接部所包括的1层聚丙烯层的厚度的值的和之比,处于75~143%的范围。即,热熔接部100所包括的1层酸改性聚丙烯层的厚度[a]和所述一体化了的聚丙烯层的厚度[b]的和[a+b]、与非熔接部200所包括的1层酸改性聚丙烯层的厚度的值[A]和非熔接部200所包括的1层聚丙烯层的厚度的值[B]的和[A+B]之比,处于75~143%。如果所述比小于75%,则在热熔接部中,作为绝缘材料的酸改性聚丙烯层和聚丙烯层变薄。其结果,电解液到金属基材为止的到达距离变短。因此,电池的绝缘性降低。此外,如果所述比例超过143%,则由于酸改性聚丙烯层和聚丙烯层较厚,所以存在热熔接部未适当地被熔接的可能性。
说明本实施方式的锂离子二次电池的其它实施方式(未图示)。优选的是,封装体的热熔接部所包括的1层酸改性聚丙烯层的厚度的值,小于封装体的非熔接部所包括的1层酸改性聚丙烯层的厚度的值。即,热熔接部所包括的1层酸改性聚丙烯层的厚度的值[a],小于非熔接部所包括的1层酸改性聚丙烯层的厚度的值[A](a<A)。通过仅在接近封装体的端部的非水电解液能向外部透过的热熔接部,使容易透过非水电解液的酸改性聚丙烯层的厚度相对于聚丙烯层的厚度足够小,由此在非熔接部,能够不会使绝缘性降低地有效地防止电解液向封装体外漏出。
各实施方式的锂离子二次电池包括正极,所述正极具有设置于正极集电体的、包含正极活性物质的正极活性物质层。优选的是,正极具有通过将包含正极活性物质、粘合剂和根据情况的导电助剂的混合物涂布或滚压在由铝箔等金属箔构成的正极集电体上后经过干燥工序得到的正极活性物质层。作为正极活性物质,可以使用锂过渡金属氧化物。作为能使用的锂过渡金属氧化物的例子,优选的是锂镍系氧化物(例如LiNiO2)、锂钴系氧化物(例如LiCoO2)、锂锰系氧化物(例如LiMn2O4)以及它们的混合物。此外,作为正极活性物质,可以使用由通式LixNiyMnzCo(1-y-z)O2表示的锂镍锰钴复合氧化物。在此,通式中的x,是满足1≦x≦1.2的关系的正数。此外,y和z是满足y+z<1的关系的正数。此外,y的值为0.5以下。另外,如果锰的比例变大,则难以合成单相的复合氧化物。因此,优选的是,满足z≦0.4的关系。此外,如果钴的比例变大,则成本增高,而且,电池的容量也减小。因此,优选的是,满足1-y-z<y和1-y-z<z的关系。从得到高容量的电池的观点出发,特别优选的是,满足y>z和y>1-y-z的关系。锂镍锰钴复合氧化物优选的是具有层状结晶构造。
作为根据情况用于正极活性物质层的导电助剂的例子,可以举出碳纳米纤维等碳纤维;乙炔黑、科琴黑等碳黑;以及活性炭、中孔碳、富勒烯类和碳纳米管等碳材料。此外,正极活性物质层可以适当包含增稠剂、分散剂和稳定剂等用于电极形成所通常使用的添加剂。
各实施方式的锂离子二次电池包括负极,所述负极具有配置在负极集电体上的、包含负极活性物质的负极活性物质层。优选的是,负极具有通过在由铜箔等金属箔构成的负极集电体上涂布或滚压包含负极活性物质、粘合剂和根据情况添加的导电助剂的混合物后经过干燥工序而得到的负极活性物质层。在本实施方式中,优选的是,负极活性物质包含石墨颗粒和/或非晶碳颗粒。如果使用包含石墨颗粒和非晶碳颗粒的混合碳材料,则电池的再生性能提高。
石墨为六方晶系六角板状晶体的碳材料。石墨也称黑铅等。优选的是,石墨具有颗粒的形状。此外,非晶碳的局部可以具有和石墨类似的结构。在此,非晶碳的意思是指具有包含随机地形成网络的微晶的结构的、作为整体是非晶质的碳材料。作为非晶碳的例子,可以举出碳黑、焦炭、活性炭、碳纤维、硬碳、软碳和中孔碳。优选的是,非晶碳具有颗粒的形状。
作为根据情况用于负极活性物质层的导电助剂的例子,可以举出碳纳米纤维等碳纤维、乙炔黑和科琴黑等碳黑、活性炭、中孔碳、富勒烯类以及碳纳米管等碳材料。此外,负极活性物质层可以适当含有增稠剂、分散剂和稳定剂等用于电极形成所通常使用的添加剂。
作为用于正极活性物质层和负极活性物质层的粘合剂的例子,可以举出聚偏氟乙烯(PVDF)、聚四氟乙烯(以下称为“PTFE”)和聚氟乙烯(以下称为“PVF”)等氟树脂;以及聚苯胺类、聚噻吩类、聚乙炔类和聚吡咯类等导电性聚合物。
作为能够用于隔离负极和正极并确保负极和正极之间的锂离子的传导性的隔膜的例子,可以举出聚乙烯和聚丙烯等聚烯烃类的多孔性膜和微孔性膜。
作为优选的电解液的例子,可以举出包含碳酸二甲酯(以下称为“DMC”)、碳酸二乙酯(以下称为“DEC”)、碳酸二正丙酯、碳酸二异丙酯、碳酸二正丁酯、碳酸二异丁酯和碳酸二叔丁酯等链状碳酸酯与碳酸丙烯酯(以下称为“PC”)和碳酸乙烯酯(以下称为“EC”)等环状碳酸酯的混合物。通过将六氟磷酸锂(LiPF6)、四氟硼酸锂(LiBF4)或者过氯酸锂(LiClO4)等锂盐溶解在所述的碳酸酯混合物中,得到电解液。
以下例示实施方式的锂离子二次电池的代表性的制作方法。
<正极的制作>
将作为正极活性物质的镍-钴-锰酸锂(例如NCM433,即镍:钴:锰=4:3:3,锂:镍=1:0.4)、作为导电助剂的碳黑粉末和作为粘合剂树脂的PVDF,以适当的固体成分质量比混合,将得到混合物添加到溶剂(例如N-甲基-2-吡咯烷酮(以下称为“NMP”))中。此外,在所述混合物中添加了有机系水分捕捉剂(例如草酸酐)。通过实施行星方式的分散混合,制备了包含均匀分散了的所述材料的浆料。将得到的浆料涂布到成为正极集电体的铝箔上。接着,通过加热涂布了的浆料,使NMP蒸发。由此,形成了正极活性物质层。此外,通过对得到的正极活性物质层进行压制,制作了具有涂布在正极集电体的单面上的正极活性物质层的正极。
<负极的制作>
作为负极活性物质,使用通过将石墨粉末和非晶碳粉末(硬碳)以适当的重量比混合得到的混合材料。将所述混合材料、作为导电助剂的碳黑粉末和作为粘合剂树脂的PVDF以适当的固体成分质量比混合,将得到的混合物添加到NMP中后进行搅拌。由此,制备了包含均匀分散在NMP中的所述材料的浆料。将得到的浆料涂布到成为负极集电体的铜箔上。接着,通过加热涂布的浆料,使NMP蒸发。由此,形成了负极活性物质层。此外,通过对得到的负极活性物质层进行压制,制作了具有涂布在负极集电体的单面上的负极活性物质层的负极。
<锂离子二次电池的制作>
将如上所述地制作成的各负极和正极分别切成合适尺寸的矩形。其中,在用于连接端子的未涂布部上超声波焊接有铝制的正极引线端子。同样地,在负极板的未涂布部上超声波焊接有与正极引线端子相同尺寸的镍制的负极引线端子。通过将所述负极板和正极板以两活性物质层隔着隔膜重叠的方式配置在包含聚丙烯的隔膜的两面上,得到电极板层叠体。另一方面,准备了作为层叠体的铝复合膜。作为铝复合膜,采用了包括层叠的聚对苯二甲酸乙二醇酯制覆盖层(厚度12μm)、尼龙制覆盖层(厚度15μm)、铝箔(厚度80μm)、酸改性聚丙烯层(厚度16μm)和聚丙烯层(厚度64μm)的复合膜。从铝复合膜切出具有比所述的正极和负极的尺寸略大尺寸的矩形。除了铝复合膜的长边的一方,其它三边通过热熔接粘合。由此,制作出袋状的封装体。热熔接时,以使热熔接部的各层的厚度维持在优选范围的方式施加适当的压力。将所述电极层叠体插入袋状的封装体。接着,向封装体内注入非水电解液(通过将PC、EC和DEC以适当的比例混合得到非水溶剂,通过将作为电解质盐的LiPF6以适当的浓度溶解到所述非水溶剂中得到溶液,将多种添加剂(甲烷二磺酸亚甲酯(MMDS)和碳酸亚乙烯酯)分别以成为1重量%浓度的方式溶解到所述溶液中,由此得到所述非水电解液)。随后,经过真空渗透工序后,在减压下通过热熔接密封开口部。由此,得到了层叠型锂离子电池。
以上,说明了本发明的实施例。但是,所述实施例只是本发明的实施方式的一个例子。所述实施例的说明并非将本发明实施方式的锂离子二次电池的技术范围限定于特定的实施方式或者具体的构成。
本发明的实施方式的锂离子二次电池,可以是以下的第一锂离子二次电池~第五锂离子二次电池。
所述第一锂离子二次电池,其是在封装体内部包括发电元件的锂离子二次电池,所述发电元件包括:正极活性物质层配置于正极集电体的正极、负极活性物质层配置于负极集电体的负极、隔膜、以及电解液,所述封装体由层叠体构成,所述层叠体是通过将金属基材、酸改性聚丙烯层和聚丙烯层依次层叠得到的,并且所述封装体的内表面是所述聚丙烯层,所述封装体具有热熔接部和非熔接部,在所述封装体的所述热熔接部,所述酸改性聚丙烯层的1层的厚度的值,小于所述聚丙烯层的厚度的二分之一的值。
所述第二锂离子二次电池,其是所述第一锂离子二次电池,其中,在所述封装体的所述热熔接部,所述聚丙烯层的厚度的二分之一的值与所述酸改性聚丙烯层的1层的厚度的值之比为2以上。
所述第三锂离子二次电池,其是所述的第一锂离子二次电池或第二锂离子二次电池,其中,所述封装体的所述热熔接部的所述酸改性聚丙烯层的1层的厚度的值和所述聚丙烯层的1层的厚度的二分之一的值的和、与所述封装体的所述非熔接部的所述酸改性聚丙烯层的1层的厚度的值和所述聚丙烯层的厚度的值的和之比为50~95%。
所述第四锂离子二次电池,其是所述的第一锂离子二次电池或第二锂离子二次电池,其中,所述封装体的所述热熔接部的所述酸改性聚丙烯层的1层的厚度的值和所述聚丙烯层的1层的厚度的值的和、与所述封装体的所述非熔接部的所述酸改性聚丙烯层的1层的厚度的值和所述聚丙烯层的厚度的值的和之比为75~143%。
所述第五锂离子二次电池,其是所述第一锂离子二次电池~第三锂离子二次电池中的任意一种锂离子二次电池,其中,所述封装体的所述热熔接部的所述酸改性聚丙烯层的1层的厚度的值,小于所述封装体的所述非熔接部的所述酸改性聚丙烯层的1层的厚度的值。
出于示例和说明的目的已经给出了所述详细的说明。根据上面的教导,许多变形和改变都是可能的。所述的详细说明并非没有遗漏或者旨在限制在这里说明的主题。尽管已经通过文字以特有的结构特征和/或方法过程对所述主题进行了说明,但应当理解的是,权利要求书中所限定的主题不是必须限于所述的具体特征或者具体过程。更确切地说,将所述的具体特征和具体过程作为实施权利要求书的示例进行了说明。
Claims (5)
1.一种锂离子二次电池,其特征在于,
所述锂离子二次电池包括封装体,在所述封装体的内部收纳有正极、负极、隔膜和电解液,
所述封装体包括层叠体,所述层叠体包括依次层叠的金属基材、酸改性聚丙烯层以及聚丙烯层,
所述聚丙烯层形成所述封装体的内表面,
所述封装体具有热熔接部和非熔接部,
所述热熔接部所包括的1层的所述酸改性聚丙烯层的厚度的值,小于所述热熔接部所包括的所述聚丙烯层的厚度的值的二分之一。
2.根据权利要求1所述的锂离子二次电池,其特征在于,所述热熔接部所包括的所述聚丙烯层的厚度的值的二分之一与所述热熔接层所包括的1层的所述酸改性聚丙烯层的厚度的值之比为2以上。
3.根据权利要求1或2所述的锂离子二次电池,其特征在于,所述热熔接部所包括的1层的所述酸改性聚丙烯层的厚度值和所述热熔接部所包括的所述聚丙烯层的厚度的值的二分之一的和、与所述非熔接部所包括的1层的所述酸改性聚丙烯层的厚度的值和所述非熔接部所包括的1层的所述聚丙烯层的厚度的值的和之比,处于50~95%的范围。
4.根据权利要求1或2所述的锂离子二次电池,其特征在于,所述热熔接部所包括的1层的所述酸改性聚丙烯层的厚度的值和所述热熔接部所包括的所述聚丙烯层的厚度的值的和、与所述非熔接部所包括的1层的所述酸改性聚丙烯层的厚度的值和所述非熔接部所包括的1层的所述聚丙烯层的厚度值的和之比,处于75~143%的范围。
5.根据权利要求1~3中任意一项所述的锂离子二次电池,其特征在于,所述热熔接部所包括的1层的所述酸改性聚丙烯层的厚度的值,小于所述非熔接部所包括的1层的所述酸改性聚丙烯层的厚度的值。
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