JP2018073474A - Battery-packaging material and battery - Google Patents
Battery-packaging material and battery Download PDFInfo
- Publication number
- JP2018073474A JP2018073474A JP2016207825A JP2016207825A JP2018073474A JP 2018073474 A JP2018073474 A JP 2018073474A JP 2016207825 A JP2016207825 A JP 2016207825A JP 2016207825 A JP2016207825 A JP 2016207825A JP 2018073474 A JP2018073474 A JP 2018073474A
- Authority
- JP
- Japan
- Prior art keywords
- layer
- packaging material
- battery
- mass
- metal layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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- B32B2457/10—Batteries
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/18—Fuel cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Ceramic Engineering (AREA)
- Mechanical Engineering (AREA)
- Sealing Battery Cases Or Jackets (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Laminated Bodies (AREA)
Abstract
Description
本発明は、電池用包装材料および電池に関するものである。 The present invention relates to a battery packaging material and a battery.
特許文献1には、最外層/バリア層/最内層、または、最外層/バリア層/中間層/最内層からなる積層体において、前記バリア層より最内層側における少なくとも一つの層間が、ドライラミネートにより積層され、更に、該上記のラミネート用接着材層が、特定の主剤と特定の硬化剤とからなる積層体が開示されている。
In
電池用包装材料の金属層にアルミニウムを使用する場合、電池内の電解液に接触することでアルミニウムとシール樹脂が剥離するおそれがある。この剥離を防止するために、アルミニウムをベーマイト処理又はクロメート処理等により表面処理する方法が知られている。しかし、製造上の観点から表面処理されてないアルミニウムを用いて、電解液に浸してもシール樹脂が金属層から剥がれない電池用包装材料を得ることが望ましい。 When aluminum is used for the metal layer of the battery packaging material, there is a possibility that the aluminum and the sealing resin may be peeled by contact with the electrolytic solution in the battery. In order to prevent this peeling, a method of surface-treating aluminum by boehmite treatment or chromate treatment is known. However, from the viewpoint of manufacturing, it is desirable to obtain a battery packaging material in which the sealing resin is not peeled off from the metal layer even when immersed in an electrolytic solution using aluminum that has not been surface-treated.
本発明の目的は、表面処理されていないアルミニウムを用いて、耐電解液性に優れる電池用包装材料及び電池を提供することにある。 An object of the present invention is to provide a battery packaging material and a battery that are excellent in electrolytic solution resistance using aluminum that is not surface-treated.
本発明の電池用包装材料は、少なくとも、基材樹脂層、金属層、及びシール樹脂層をこの順で含む積層体からなる電池用包装材料であって、
前記金属層が表面処理されていないアルミニウムからなり、
前記シール樹脂層が前記金属層に直接貼り合されており、
前記シール樹脂層が1以上の層を有し、
前記1以上の層のうちの前記金属層に接触する層が、リン酸マグネシウム、酸化マグネシウム及び有機アミンを含む組成物を含有する。
The battery packaging material of the present invention is a battery packaging material comprising a laminate including at least a base resin layer, a metal layer, and a seal resin layer in this order,
The metal layer is made of non-surface-treated aluminum;
The sealing resin layer is directly bonded to the metal layer;
The sealing resin layer has one or more layers;
The layer in contact with the metal layer among the one or more layers contains a composition containing magnesium phosphate, magnesium oxide and an organic amine.
また、本発明の電池は、上記電池用包装材料から形成された包装容器内に、少なくとも正極、負極、及び電解質を収容し、各電極からのリード線を外側に導出させた状態で周辺部をシールしてなる。 Further, the battery of the present invention contains at least the positive electrode, the negative electrode, and the electrolyte in the packaging container formed from the battery packaging material, and the peripheral portion is in a state in which the lead wire from each electrode is led out to the outside. Sealed.
本発明によれば、表面処理されていないアルミニウムを用いて、耐電解液性に優れる電池用包装材料及び電池を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the packaging material for batteries and battery which are excellent in electrolyte solution resistance can be provided using the aluminum which is not surface-treated.
[本発明の実施形態の説明]
最初に本発明の実施形態の内容を列記して説明する。
本願発明の実施形態に係る電池用包装材料は、
(1)少なくとも、基材樹脂層、金属層、及びシール樹脂層をこの順で含む積層体からなる電池用包装材料であって、
前記金属層が表面処理されていないアルミニウムからなり、
前記シール樹脂層が前記金属層に直接貼り合されており、
前記シール樹脂層が1以上の層を有し、
前記1以上の層のうちの前記金属層に接触する層が、リン酸マグネシウム、酸化マグネシウム及び有機アミンを含む組成物を含有する。
この構成によれば、表面処理されていないアルミニウムを用いて、耐電解液性に優れる電池用包装材料を提供することができる。
[Description of Embodiment of the Present Invention]
First, the contents of the embodiment of the present invention will be listed and described.
The battery packaging material according to the embodiment of the present invention is:
(1) A battery packaging material comprising a laminate including at least a base resin layer, a metal layer, and a seal resin layer in this order,
The metal layer is made of non-surface-treated aluminum;
The sealing resin layer is directly bonded to the metal layer;
The sealing resin layer has one or more layers;
The layer in contact with the metal layer among the one or more layers contains a composition containing magnesium phosphate, magnesium oxide and an organic amine.
According to this structure, the packaging material for batteries excellent in electrolyte solution resistance can be provided using the aluminum which is not surface-treated.
(2)また、(1)の電池用包装材料は、
前記金属層に接触する層が、さらにホスホン酸カルシウムを含む組成物を含有してもよい。
この構成によれば、より耐電解液性に優れる電池用包装材料を提供することができる。
(2) The battery packaging material of (1)
The layer in contact with the metal layer may further contain a composition containing calcium phosphonate.
According to this structure, the packaging material for batteries which is more excellent in electrolyte solution resistance can be provided.
(3)また、(1)又は(2)の電池用包装材料は、
前記金属層に接触する層が、さらにリン酸亜鉛を含む組成物を含有してもよい。
この構成によれば、より耐電解液性に優れる電池用包装材料を提供することができる。
(3) The battery packaging material of (1) or (2)
The layer in contact with the metal layer may further contain a composition containing zinc phosphate.
According to this structure, the packaging material for batteries which is more excellent in electrolyte solution resistance can be provided.
(4)また、(1)〜(3)のいずれかの電池用包装材料は、
前記金属層に接触する層が、前記リン酸マグネシウム、酸化マグネシウム及び有機アミンを含む組成物を、3質量%以上8質量%以下の割合で含有してもよい。
この構成によれば、特に耐電解液性に優れる電池用包装材料を提供することができる。
(4) The battery packaging material according to any one of (1) to (3)
The layer in contact with the metal layer may contain the composition containing the magnesium phosphate, magnesium oxide, and organic amine in a proportion of 3% by mass to 8% by mass.
According to this configuration, it is possible to provide a battery packaging material that is particularly excellent in electrolytic solution resistance.
(5)また、(2)の電池用包装材料は、
前記リン酸マグネシウム、酸化マグネシウム及び有機アミンを含む組成物と、前記ホスホン酸カルシウムを含む組成物との質量比が、1:2〜2:1でもよい。
この構成によれば、特に耐電解液性に優れる電池用包装材料を提供することができる。
(5) The battery packaging material of (2)
The mass ratio of the composition containing the magnesium phosphate, magnesium oxide and organic amine and the composition containing the calcium phosphonate may be 1: 2 to 2: 1.
According to this configuration, it is possible to provide a battery packaging material that is particularly excellent in electrolytic solution resistance.
(6)また、(3)の電池用包装材料は、
前記リン酸マグネシウム、酸化マグネシウム及び有機アミンを含む組成物と、前記リン酸亜鉛を含む組成物との質量比が、1:2〜2:1でもよい。
この構成によれば、特に耐電解液性に優れる電池用包装材料を提供することができる。
(6) The battery packaging material of (3)
The mass ratio of the composition containing the magnesium phosphate, magnesium oxide and organic amine and the composition containing the zinc phosphate may be 1: 2 to 2: 1.
According to this configuration, it is possible to provide a battery packaging material that is particularly excellent in electrolytic solution resistance.
また、本願発明の実施形態に係る電池は、
(7)(1)〜(6)のいずれかの電池用包装材料から形成された包装容器内に、少なくとも正極、負極、及び電解質を収容し、各電極からのリード線を外側に導出させた状態で周辺部をシールしてなる。
この構成によれば、耐電解液性に優れる電池を提供することができる。
The battery according to the embodiment of the present invention is
(7) At least a positive electrode, a negative electrode, and an electrolyte are accommodated in a packaging container formed of the battery packaging material according to any one of (1) to (6), and lead wires from each electrode are led out to the outside. The periphery is sealed in a state.
According to this configuration, it is possible to provide a battery having excellent electrolytic solution resistance.
[本発明の実施形態の詳細]
1.電池用包装材料
本発明の実施形態に係る電池用包装材料1は、少なくとも、基材樹脂層11、金属層13、及びシール樹脂層14をこの順に有する積層体からなる。この積層体は、例えば、ヒートシールにより袋状の容器を形成し、又は深絞り成形によりカップ状やトレー状の容器を形成することができるシートである。図1に示すように、本実施形態の電池用包装材料1は、基材樹脂層11と金属層13との間に接着層12を有していてもよい。電池の組み立て時に、電池素子の周縁に位置するシール樹脂層14同士を熱溶着することにより電池素子が封止される。
[Details of the embodiment of the present invention]
1. Battery Packaging Material A
(1)基材樹脂層
本実施形態の電池用包装材料1において、基材樹脂層11は最外層を形成する層である。基材樹脂層11は、単層でも、2層以上の多層でもよい。基材樹脂層11を多層構造にする場合、各層はそれぞれ異なる樹脂から形成されてもよい。多層構造の場合の各層は、接着剤を介して接着してもよく、また接着剤を介さず直接積層させてもよい。
(1) Base resin layer In the
基材樹脂層11を形成する樹脂については、絶縁性を備えるものであることを限度として特に限定されないが、例えば、ポリエステル、ポリアミド、エポキシ樹脂、アクリル樹脂、フッ素樹脂、ポリウレタン及びこれらの混合物等が挙げられる。好ましくはポリエステル、ポリアミドが挙げられる。
The resin forming the
ポリエステルとしては、例えば、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレート、ポリブチレンナフタレート、共重合ポリエステル、ポリカーボネートが挙げられるが、これらに限定されない。ポリアミドとしては、例えば、ナイロン6、ナイロン66、ナイロン6とナイロン66との共重合体、ナイロン610、ポリメタキシリレンアジパミド(MXD6)が挙げられるが、これらに限定されない。 Examples of the polyester include, but are not limited to, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, copolymerized polyester, and polycarbonate. Examples of the polyamide include, but are not limited to, nylon 6, nylon 66, a copolymer of nylon 6 and nylon 66, nylon 610, and polymetaxylylene adipamide (MXD6).
基材樹脂層11は、1軸又は2軸延伸された樹脂フィルムで形成されていてもよく、また未延伸の樹脂フィルムで形成してもよい。延伸された樹脂フィルム、とりわけ2軸延伸された樹脂フィルムは、配向結晶化することにより耐熱性が向上しているので、基材樹脂層11として好適に使用される。また、基材樹脂層11は、上記の素材を金属層13上にコーティングして形成されていてもよい。
The
基材樹脂層11の厚さは、通常5〜40μm、好ましくは10〜35μm、より好ましくは15〜30μm程度である。基材樹脂層11の厚みが薄すぎると、ピンホールが発生する恐れがある。
The thickness of the
本実施形態の電池用包装材料1において、接着層12は、基材樹脂層11と金属層13とを接着させるために、必要に応じて設けられる層である。
In the
接着層12は、基材樹脂層11と金属層13とを接着可能である接着剤によって形成される。接着層12の形成に使用される接着剤は、2液硬化型接着剤であってもよく、また1液硬化型接着剤であってもよい。更に、接着層12の形成に使用される接着剤の接着機構についても、特に制限されず、化学反応型、溶剤揮発型、熱溶融型、熱圧型等のいずれであってもよい。
The
接着層12の形成には、ポリエステル系、ポリエチレンイミン系、ポリエーテル系、シアノアクリレート系、ウレタン系、有機チタン系、ポリエーテルウレタン系、エポキシ系、ポリエステルポリウレタン系、イミド系、イソシアネート系、ポリオレフィン系、シリコーン系の各種接着剤を用いることができる。
For the formation of the
接着層12の厚さは、通常2〜50μm、好ましくは3〜25μm程度である。
The thickness of the
(2)金属層
本実施形態の電池用包装材料1において、金属層13は、包装材料の強度向上の他、電池内部に水蒸気、酸素、光等が侵入するのを防止するためのバリア層として機能する層である。金属層13を形成する金属は、表面処理されていないアルミニウムである。ここでいう、表面処理とはアルミニウムの表面に酸化被膜や樹脂被膜等を形成する処理や表面積を広げる処理であり、例えば、硝酸クロム、フッ化クロム、硫酸クロム、酢酸クロム等のクロム酸化合物を用いたクロム酸クロメート処理;リン酸ナトリウム、リン酸カリウム等のリン酸化合物を用いたリン酸クロメート処理;ベーマイト処理;有機酸を含む物質による化成処理;又は粗面化処理等を指す。
(2) Metal layer In the
金属層13の厚さは、通常10〜200μm、好ましくは20〜100μm程度である。
The thickness of the
(3)シール樹脂層
本実施形態の電池用包装材料1において、シール樹脂層14は、最内層に該当し、電池の組み立て時にシール樹脂層14同士が熱溶着して電池素子を密封する層である。シール樹脂層14は、単層でも、2層以上の多層でもよい。シール樹脂層14を多層構造にする場合、各層はそれぞれ異なる樹脂から形成されてもよい。多層構造の場合の各層は、接着剤を介して接着してもよく、また接着剤を介さず直接積層させてもよい。シール樹脂層14は、金属層13に直接貼り合されている。
(3) Seal resin layer In the
シール樹脂層14を構成する樹脂としては、ポリオレフィン、酸変性ポリオレフィン及びこれらの混合物等が挙げられる。ポリオレフィンとしては、低密度、中密度、高密度ポリエチレン、直鎖状低密度ポリエチレン、ホモポリプロピレン及びプロピレンとエチレン又は他のαオレフィンとのランダム又はブロック共重合体等が挙げられる。酸変性ポリオレフィンとは、カルボン酸により上記のポリオレフィンを変性したものである。変性に使用されるカルボン酸としては、マレイン酸、アクリル酸、イタコン酸、クロトン酸、無水マレイン酸などが挙げられる。上記の中でも、酸変性ポリオレフィンが好ましく、酸変性ポリプロピレンがより好ましい。
Examples of the resin constituting the sealing
シール樹脂層14のうちの金属層13に接触している層は、リン酸マグネシウム、酸化マグネシウム及び有機アミンを含む組成物(以下、組成物(1)とする。)を含有する。この特定の組成物を含有することで、電解液と接触することによるシール樹脂層14の金属層13からの剥離を抑制することができる。
The layer in contact with the
前述の金属層13に接触している層は、組成物(1)を3質量%〜8質量%の割合で含有するとよい。これによれば、金属層13を表面処理しなくてもシール樹脂層14が金属層13からより剥離しにくくなる。組成物(1)の含有量が3質量%未満であると、剥離が生じるおそれがあり、8質量%より多いと当該層の見た目や強度に悪影響を及ぼすおそれがあり好ましくない。
The layer in contact with the
また、組成物(1)は、リン酸マグネシウムを5質量%〜65質量%、酸化マグネシウムを5質量%〜50質量%、有機アミンを3質量%〜50質量%の割合で含有することが好ましく、リン酸マグネシウム、酸化マグネシウム及び有機アミンを合計で99質量%以上の割合で含有することが好ましい。有機アミンには、複素環式アミンやアルコール基含有アミンが挙げられる。複素環式アミンには、モルホリン、ヘキサメチレンテトラミン、トリエノールアミンなどが挙げられる。 The composition (1) preferably contains 5% to 65% by weight of magnesium phosphate, 5% to 50% by weight of magnesium oxide, and 3% to 50% by weight of organic amine. It is preferable to contain magnesium phosphate, magnesium oxide and organic amine in a proportion of 99% by mass or more in total. Organic amines include heterocyclic amines and alcohol group-containing amines. Heterocyclic amines include morpholine, hexamethylenetetramine, trienolamine, and the like.
また、前述の金属層13に接触している層は、組成物(1)と併せて、ホスホン酸カルシウムを含む組成物(以下、組成物(2)とする。)を含有してもよい。この特定の組成物をさらに含有することで、電解液と接触することによるシール樹脂層14と金属層13との剥離をより抑制することができる。
The layer in contact with the
組成物(2)はホスホン酸カルシウム以外にSiO2、CaSiO3、CaCO3を含んでもよい。この場合、組成物(2)は、CaHO3P(ホスホン酸カルシウム)を1質量%〜30質量%、好ましくは5質量%〜15質量%、SiO2を1質量%〜30質量%、好ましくは5質量%〜15質量%、CaSiO3を1質量%〜30質量%、好ましくは5質量%〜15質量%、CaCO3を10質量%〜97質量%、好ましくは55質量%〜85質量%の質量比で含有するとよい。 The composition (2) may contain SiO 2 , CaSiO 3 , and CaCO 3 in addition to calcium phosphonate. In this case, the composition (2) comprises CaHO 3 P (calcium phosphonate) in an amount of 1% by mass to 30% by mass, preferably 5% by mass to 15% by mass, and SiO 2 in an amount of 1% by mass to 30% by mass, preferably 5% by mass to 15% by mass, 1% by mass to 30% by mass of CaSiO 3 , preferably 5% by mass to 15% by mass, and 10% by mass to 97% by mass of CaCO 3 , preferably 55% by mass to 85% by mass. It is good to contain by mass ratio.
また、この場合、組成物(1)と組成物(2)の質量比は1:2〜2:1であることが好ましい。 In this case, the mass ratio of the composition (1) to the composition (2) is preferably 1: 2 to 2: 1.
また、前述の金属層13に接触している層は、組成物(1)と併せて、リン酸亜鉛を含む組成物(以下、組成物(3)とする。)を含有してもよい。この特定の組成物をさらに含有することで、電解液と接触することによるシール樹脂層14と金属層13との剥離をより抑制することができる。
The layer in contact with the
組成物(3)は、リン酸亜鉛以外にSiO2、CaSiO3、CaCO3を含んでもよい。この場合、組成物(3)は、Zn3(PO4)2(リン酸亜鉛)を10質量%〜97質量%、好ましくは70質量%〜97質量%、SiO2を1質量%〜30質量%、好ましくは1質量%〜10質量%、CaSiO3を1質量%〜30質量%、好ましくは1質量%〜10質量%、CaCO3を1質量%〜30質量%好ましくは1質量%〜10質量%の質量比で含有するとよい。 The composition (3) may contain SiO 2 , CaSiO 3 , and CaCO 3 in addition to zinc phosphate. In this case, the composition (3) comprises 10% by mass to 97% by mass, preferably 70% by mass to 97% by mass of Zn 3 (PO 4 ) 2 (zinc phosphate), and 1% by mass to 30% by mass of SiO 2. %, Preferably 1% by mass to 10% by mass, CaSiO 3 by 1% by mass to 30% by mass, preferably 1% by mass to 10% by mass, and CaCO 3 by 1% by mass to 30% by mass, preferably 1% by mass to 10% by mass. It is good to contain by the mass ratio of the mass%.
また、この場合、組成物(1)と組成物(3)の質量比は1:2〜2:1であることが好ましい。 In this case, the mass ratio of the composition (1) to the composition (3) is preferably 1: 2 to 2: 1.
そして、シール樹脂層14のうちの金属層13に接触している層は、組成物(1)と併せて、組成物(2)及び組成物(3)の両方を含有してもよい。この場合、組成物(1)と組成物(2)の質量比は1:2〜2:1、組成物(1)と組成物(3)の質量比は1:2〜2:1であることが好ましい。
And the layer which is contacting the
なお、シール樹脂層14のうちの金属層13に接触している層以外の層が、前述の組成物(1)〜組成物(3)を含有していてもよい。
In addition, layers other than the layer in contact with the
シール樹脂層14の厚みは、通常3〜40μm、好ましくは20〜40μm程度である。また、シール樹脂層には、必要に応じて、無機フィラー、可塑剤、熱安定剤、光安定剤、撥水剤、吸水剤、滑材、カップリング剤、顔料、染料などの各種添加剤を配合することができる。
The thickness of the sealing
2.電池
本実施形態の電池は、本実施形態の電池用包装材料を用いて形成した包装容器内に、正極、負極、電解質などの電池素子を収容し、各電極からのリード線を開口部から外側に導出させた状態で、該開口部をヒートシールした構造を有するものである。
2. Battery The battery of the present embodiment accommodates battery elements such as a positive electrode, a negative electrode, and an electrolyte in a packaging container formed using the battery packaging material of the present embodiment, and leads from each electrode to the outside from the opening. In this state, the opening is heat sealed.
図2に示すように、本実施形態の電池用包装材料1を2枚貼り合わせ、一辺に開口部を設けるように周縁部をヒートシールして包装容器を形成し、包装容器の内部に電池素子を収容して、各電極からのリード線22を開口部から外側に導出させた状態で、該開口部をヒートシールすることで、本実施形態の電池2を作製することができる。また、本実施形態の電池用包装材料1と、当該包装材料1の周縁部以外を凹型にした電池用包装材料101とを用いて、図4に示す形状の電池102を作製することもできる。さらに、本実施形態の電池用包装材料1の1枚を折りたたんで使用して、図5に示す形状の電池202を作製することもできる。
As shown in FIG. 2, two
本実施形態の電池は、一次電池、二次電池のいずれでもあり得る。特に二次電池である場合、例えば、リチウムイオン電池、リチウムイオンポリマー電池、鉛畜電池、ニッケル・水素畜電池、ニッケル・カドミウム畜電池、ニッケル・鉄畜電池、ニッケル・亜鉛畜電池、酸化銀・亜鉛畜電池、金属空気電池、多価カチオン電池、コンデンサー、キャパシタ等であり得る。 The battery of this embodiment can be either a primary battery or a secondary battery. In particular, in the case of a secondary battery, for example, lithium ion battery, lithium ion polymer battery, lead live battery, nickel / hydrogen live battery, nickel / cadmium live battery, nickel / iron live battery, nickel / zinc live battery, silver oxide / It can be a zinc livestock battery, a metal-air battery, a polyvalent cation battery, a capacitor, a capacitor, or the like.
次に発明を実施するための形態を実施例により説明する。実施例は本発明の範囲を限定するものではない。 Next, modes for carrying out the invention will be described by way of examples. The examples are not intended to limit the scope of the invention.
(例1)
厚さ40μmのアルミニウム箔に、基材樹脂層としてナイロン6を用いて形成された厚み25μmの延伸フィルムをドライラミネーション法により貼り合わせて多層シートを作製した。接着剤の厚みは、4μmであった。アルミニウム箔には、表面処理を施さなかった。
次に、押出成型により、酸変性ランダムポリプロピレンを主成分とし、総質量に対してリン酸マグネシウム、酸化マグネシウム及び有機アミンを含む組成物を5質量%の割合で含有するシール樹脂層を作製した。当該リン酸マグネシウム、酸化マグネシウム及び有機アミンを含む組成物としては、リン酸マグネシウムを59質量%、酸化マグネシウムを36質量%、有機アミンを4質量%の割合で含有する組成物を使用した。
前記多層シートのアルミニウム箔面とシール樹脂層とを対向させて、熱ラミネーション法により電池用包装材料を作成した。シール樹脂層の厚みは35μmであり、全体の厚みは約105μmであった。
(Example 1)
A multi-layer sheet was prepared by laminating a stretched film having a thickness of 25 μm formed using nylon 6 as a base resin layer on an aluminum foil having a thickness of 40 μm by a dry lamination method. The thickness of the adhesive was 4 μm. The aluminum foil was not surface treated.
Next, a sealing resin layer containing 5% by mass of a composition containing acid-modified random polypropylene as a main component and containing magnesium phosphate, magnesium oxide and an organic amine based on the total mass was produced by extrusion molding. As the composition containing magnesium phosphate, magnesium oxide, and organic amine, a composition containing 59% by mass of magnesium phosphate, 36% by mass of magnesium oxide, and 4% by mass of organic amine was used.
A battery packaging material was prepared by a thermal lamination method with the aluminum foil surface of the multilayer sheet facing the seal resin layer. The thickness of the sealing resin layer was 35 μm, and the total thickness was about 105 μm.
(例2)
シール樹脂層として、酸変性ランダムポリプロピレンを主成分とし、総質量に対してリン酸マグネシウム、酸化マグネシウム及び有機アミンを含む組成物を4質量%、ホスホン酸カルシウムを含む組成物を2質量%の割合で含有する樹脂を用いた以外は、例1と同様である電池用包装材料を作成した。当該ホスホン酸カルシウムを含む組成物としては、CaHO3Pを10質量%、SiO2を10質量%、CaSiO3を10質量%、CaCO3を70質量%の割合で含有する組成物を使用した。
(Example 2)
As a sealing resin layer, a proportion of 4% by mass of a composition containing magnesium phosphate, magnesium oxide and an organic amine and 2% by mass of a composition containing calcium phosphonate based on the total mass of acid-modified random polypropylene. A battery packaging material was prepared in the same manner as in Example 1 except that the resin contained in was used. Compositions comprising the calcium phosphonate, CaHO 3 P 10 mass%, were used SiO 2 10 wt%, CaSiO 3 to 10 wt%, a composition containing a proportion of CaCO 3 70% by weight.
(例3)
シール樹脂層として、酸変性ランダムポリプロピレンを主成分とし、総質量に対してリン酸マグネシウム、酸化マグネシウム及び有機アミンを含む組成物を3質量%、ホスホン酸カルシウムを含む組成物を3質量%の割合で含有する樹脂を用いた以外は、例2と同様である電池用包装材料を作成した。
(Example 3)
As a sealing resin layer, a proportion of 3% by mass of a composition containing acid-modified random polypropylene as a main component and containing magnesium phosphate, magnesium oxide and an organic amine and 3% by mass of a composition containing calcium phosphonate with respect to the total mass. A battery packaging material was prepared in the same manner as in Example 2 except that the resin contained in was used.
(例4)
シール樹脂層として、酸変性ランダムポリプロピレンを主成分とし、総質量に対してリン酸マグネシウム、酸化マグネシウム及び有機アミンを含む組成物を3質量%、リン酸亜鉛を含む組成物を3質量%の割合で含有する樹脂を用いた以外は、例1と同様である電池用包装材料を作成した。当該リン酸亜鉛を含む組成物としては、Zn3(PO4)2を80質量%、SiO2を5質量%、CaSiO3を5質量%、CaCO3を10質量%の割合で含有する組成物を使用した。
(Example 4)
As a sealing resin layer, a composition containing acid-modified random polypropylene as a main component, 3% by mass of a composition containing magnesium phosphate, magnesium oxide and an organic amine with respect to the total mass, and 3% by mass of a composition containing zinc phosphate A battery packaging material was prepared in the same manner as in Example 1 except that the resin contained in was used. As the composition containing the zinc phosphate, a composition containing Zn 3 (PO 4 ) 2 at 80% by mass, SiO 2 at 5% by mass, CaSiO 3 at 5% by mass, and CaCO 3 at 10% by mass. It was used.
(例5)
シール樹脂層として、酸変性ランダムポリプロピレンから成る樹脂を用いた以外は、例1と同様である電池用包装材料を作成した。
(Example 5)
A battery packaging material similar to that of Example 1 was prepared except that a resin made of acid-modified random polypropylene was used as the sealing resin layer.
(剥離性評価)
作製した電池用包装材料(例1〜例5)を横8cm×縦8cmのシート片に切り出し、このシート片を縦方向に二つ折りにして、対向する2辺を1cm幅でシールして、開口部を有する包装体を作製した。この包装体に、以下の電解液を充填して開口部を0.5cm幅で密封シールしてから所定時間経過後、180度ピール試験を行った。電解液として、リチウムイオン二次電池の電解液に利用されているものを用意した。ここでは、電解質がLiPF6(電解質のモル濃度1mol/L)、溶媒がEC:DMC:DEC=1:1:1(V/V)の混合有機溶媒であるもの(キシダ化学株式会社製電解液)を用意した。V/Vは、体積比を意味する。恒温槽を利用して、電解液の温度を65℃に維持した。
(Peelability evaluation)
The produced battery packaging materials (Examples 1 to 5) were cut into 8 cm wide × 8 cm long sheet pieces, the sheet pieces were folded in the vertical direction, and the two opposing sides were sealed with a width of 1 cm, and opened. The package which has a part was produced. The package was filled with the following electrolytic solution, and the opening was hermetically sealed with a width of 0.5 cm. After a predetermined time had elapsed, a 180 degree peel test was performed. As an electrolytic solution, one used for an electrolytic solution of a lithium ion secondary battery was prepared. Here, the electrolyte is LiPF6 (molar concentration of
所定時間経過後、包装体の開口部のシール部を切断して電解液を取り除き、包装体を横1cm、縦5cmのシート片に切り出して、縦方向末端のシール樹脂層をアルミニウムから少しだけ剥がし、つかみしろを確保した。そして、引張試験装置に把持して、互いに反対方向に引っ張り、シール樹脂層とアルミニウムの180度剥離強度を測定した。また、電解液に浸漬させていない包装材料の、シール樹脂層とアルミニウムの180度剥離強度も測定した。 After a predetermined time has passed, the sealing part at the opening of the package is cut to remove the electrolyte, the package is cut into 1 cm wide and 5 cm long sheet pieces, and the seal resin layer at the end in the vertical direction is peeled off slightly from the aluminum. , Secured the margin. And it hold | gripped in the tension test apparatus and it pulled in the mutually opposite direction, and measured 180 degree | times peeling strength of the sealing resin layer and aluminum. Further, the 180 degree peel strength between the sealing resin layer and aluminum of the packaging material not immersed in the electrolytic solution was also measured.
長さ20mm剥がす時の最大強度(単位N)をアルミニウムの幅で割った値(単位はN/cm)を剥離強度として算出し、これが15以上のものをA、5以上15未満のものをB、5未満のものをCとした。また、密着が強く、剥離試験で材料が破壊されてしまったものは材破と表現した。結果を表1に示す。 The value obtained by dividing the maximum strength (unit N) when peeling 20 mm in length by the width of the aluminum (unit: N / cm) is calculated as the peel strength. Those less than 5 were designated as C. In addition, the case where the adhesion was strong and the material was destroyed in the peel test was expressed as material failure. The results are shown in Table 1.
例1〜例4では、剥離強度が強く、電解液との接触による密着性の低下が抑制されているとわかる。これに対し、例5においては電解液と接触させることにより剥離強度が弱くなり、層間の密着性が低下していることがわかる。 In Examples 1 to 4, it can be seen that the peel strength is strong and a decrease in adhesion due to contact with the electrolytic solution is suppressed. On the other hand, in Example 5, it turns out that peeling strength becomes weak by making it contact with electrolyte solution, and the adhesiveness between layers falls.
これらの結果より、本実施形態の樹脂フィルムを使用した電池用包装材料は、表面処理を施していないアルミニウムを使用していても、電解液との接触による樹脂フィルムの剥離を抑制することができ、良好な耐電解液性を有することがわかる。 From these results, the battery packaging material using the resin film of the present embodiment can suppress the peeling of the resin film due to contact with the electrolytic solution even when using aluminum that has not been surface-treated. It can be seen that it has good resistance to electrolytic solution.
1,101:電池用包装材料
11:基材樹脂層
12:接着層
13:金属層
14:シール樹脂層
2,102,202:電池
21:リード線
DESCRIPTION OF SYMBOLS 1,101: Battery packaging material 11: Base resin layer 12: Adhesive layer 13: Metal layer 14:
Claims (7)
前記金属層が表面処理されていないアルミニウムからなり、
前記シール樹脂層が前記金属層に直接貼り合されており、
前記シール樹脂層が1以上の層を有し、
前記1以上の層のうちの前記金属層に接触する層が、リン酸マグネシウム、酸化マグネシウム及び有機アミンを含む組成物を含有する、
電池用包装材料。 A battery packaging material comprising a laminate including at least a base resin layer, a metal layer, and a seal resin layer in this order,
The metal layer is made of non-surface-treated aluminum;
The sealing resin layer is directly bonded to the metal layer;
The sealing resin layer has one or more layers;
The layer in contact with the metal layer of the one or more layers contains a composition comprising magnesium phosphate, magnesium oxide and an organic amine.
Battery packaging material.
In the packaging container formed from the battery packaging material according to any one of claims 1 to 6, at least a positive electrode, a negative electrode, and an electrolyte are accommodated, and lead wires from each electrode are led out to the outside. A battery that has its peripheral part sealed in a wet state.
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JP2001176464A (en) * | 1999-12-17 | 2001-06-29 | Sumitomo Electric Ind Ltd | Nonaqueous electrolyte battery |
JP2008287971A (en) * | 2007-05-16 | 2008-11-27 | Sony Corp | Layered package material, outer package material for battery, and the battery |
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