TW202008629A - 蓄電裝置用外裝材及其製造方法 - Google Patents
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Abstract
本發明係提供一種蓄電裝置用外裝材(1),其以積層狀具備最外層(2)、密封層(4)及配置於兩層(2、4)間之屏蔽層(3)。最外層(2),是由選自聚醯胺薄膜、聚酯薄膜及聚烯烴薄膜所成群中至少一種所成。最外層(2)之表面(2a)之表面性狀中,算術平均高度Sa之範圍為0.03~0.20μm。當將由Sa的基準面+0.1μm之高度位置的截面積為7500μm2以上之凸部定義為山時,山之數量範圍為每1mm2 5~30個。
Description
本發明係關於鋰離子電池等之蓄電裝置用外裝材、其製造方法及蓄電裝置。
例如作為鋰離子電池用之外裝材,有由以積層狀具備最外層、屏蔽層及密封層之積層薄膜所形成之物。於使用此外裝材製造鋰離子電池之情形,外裝材形成為袋狀或藉由使用成形金屬模之成形加工形成為容器狀,且於其內部收容有鋰離子電池內容物(單電池、電解液等)並進行熱密封。
使用此外裝材之鋰離子電池,在使用之時被組入指定之迴路或被安裝至指定之安裝地點。此時,為了使鋰離子電池的位置不發生偏移,一般而言會以絕緣性黏著帶固定鋰離子電池。
但是,為了使外裝材之成形性及滑動性良好,或是為了應付黏連問題,傳統的外裝材表面有時會存在潤滑劑或防黏連劑(例如參照專利文獻1)。
【專利文獻1】日本專利第5652178號公報
在如上所述,外裝材之表面存在潤滑劑或防黏連劑之情形,外裝體表面與黏著帶之密著性下降,在以黏著帶固定鋰離子電池的位置時有時會發生黏著帶自外裝材表面剝落的狀況。
本發明係鑒於上述技術背景而成者,其目的在於提供一種具有滑動性高且與黏著帶之密著性亦高之表面之蓄電裝置用外裝材。
本發明之其他目的,可由以下之較佳實施型態中明瞭。
本發明人在針對蓄電裝置用外裝材進行深入研究調查後,發現只要係外裝材之最外層是由指定之薄膜所成,進一步,最外層之表面之表面性狀中,算術平均高度Sa在指定的範圍內且存在於該表面之多數之凸部中,每1mm2中之指定大小之凸部的數量在指定的範圍內者,就可達成上述目的,進而完成了本發明。
亦即,本發明提供以下之技術手段。
1)一種蓄電裝置用外裝材,其以積層狀具備最外層、密封層、及配置於前述兩層間之屏蔽層,其特徵係: 前述最外層,是由選自聚醯胺薄膜、聚酯薄膜及聚烯烴薄膜所成群中至少一種所成;前述最外層之表面之表面性狀中,算術平均高度Sa之範圍為0.03~0.20μm,當由前述Sa的基準面+0.1μm之高度位置的截面積為7500μm2以上之凸部定義為山時,山之數量範圍為每1mm2 5~30個。
2)如前項1所記載之蓄電裝置用外裝材,其中,當前述山中由前述基準面+0.1μm之高度位置之截面的重心位置定義為前述山之重心位置時,存在於1mm2中相互鄰近之前述山之重心位置間的距離範圍皆為150~700μm。
3)如前項1或2所記載之蓄電裝置用外裝材,其中,前述最外層及前述屏蔽層,是以配置於此兩層間之接著劑層接著,且前述接著劑層之面向前述最外層側的面形成為凹凸狀。
4)如前項3所記載之蓄電裝置用外裝材,其中,形成於前述接著劑層之面向前述最外層側的面之凹凸處,與形成於前述最外層之表面之凹凸處大略一致。
5)一種蓄電裝置用外裝材之製造方法,其是如前項3所記載之蓄電裝置用外裝材之製造方法,其特徵係:藉由凹版塗佈法將外裝材中配置於最外層與屏蔽層之間之接著劑層之接著劑塗佈至屏蔽層上。
6)一種蓄電裝置,其特徵係以如前項1至4中任一項所記載之蓄電裝置用外裝材包裝蓄電裝置內容物。
本發明具有以下之發明功效。
前項1中,由於外裝材之最外層是由選自聚醯胺薄膜、聚酯薄膜及聚烯烴薄膜所成群中至少一種所成,且最外層之表面之算術平均高度Sa之範圍為0.03~0.20μm,山的數量範圍為每1mm2 5~30個,作為最外層之表面之外裝材表面,在藉由形成有凹凸部而具有高滑動性的同時,藉由表面積擴大而使與黏著帶之接著面積變大,從而在外裝材表面之與黏著帶之密著性方面亦具有高密著性。
前項2~4中,可確實地提高外裝材表面之滑動性,亦可確實地提高外裝材表面之與黏著帶之密著性。
前項5中,藉由將接著劑層之接著劑以凹版塗佈法塗佈至屏蔽層上,可使本發明之蓄電裝置用外裝材之最外層之表面確實地實現指定之表面性狀。
前項6中,可提供一種能以黏著帶牢固地固定位置之蓄電裝置。
1‧‧‧外裝材
2‧‧‧最外層
2a‧‧‧最外層之表面
3‧‧‧屏蔽層
4‧‧‧密封層
5‧‧‧外側接著劑層
5a‧‧‧外側接著劑層面向最外層側的面
6‧‧‧內側接著劑層
8‧‧‧山
10‧‧‧正方形區域之外周邊界線
C‧‧‧山之重心位置
d1~d11‧‧‧相互鄰近之山之重心位置間的距離
S‧‧‧正方形區域
【圖1】本發明之一實施型態之蓄電裝置用外裝材之概略截面圖。
【圖2】顯示外裝材的最外層的表面之表面凹凸像中由Sa的基準面+0.1μm之高度的等高線之概略圖。
【圖3】說明圖2所示之概略圖中相互鄰近之山之重心位置間的距離之圖。
以下參照圖式針對本發明之一實施型態進行說明。
如圖1所示,本發明之一實施型態之蓄電裝置用外裝材1,為用於蓄電裝置,例如用於鋰離子電池者,且其如同傳統之外裝材,形成為袋狀或藉由使用成形金屬模之成形加工形成為容器狀,其內部收容有作為蓄電裝置內容物之鋰離子電池內容物(單電池、電解液等)並被熱密封。
如圖1所示,外裝材1是以積層狀具備最外層2、作為最內層之密封層4、及配置於兩層2、4間之屏蔽層3,且是由此等層2~4接著一體化後之積層薄膜所成。
若詳述外裝材1之構成,則最外層2及屏蔽層3是藉由配置於兩層2、3間之外側接著劑層5相互接著,屏蔽層3及密封層4是藉由配置於兩層3、4間之內側接著劑層6相互接著。
最外層2,亦被稱作外裝材1之基材層,是由選自聚醯胺薄膜、聚酯薄膜及聚烯烴薄膜所成群中至少一種所成。
聚醯胺薄膜,可適宜地使用二軸延伸尼龍薄膜(例如:二軸延伸6尼龍薄膜)等。
聚酯薄膜,可使用聚對苯二甲酸乙二酯薄膜(PET薄膜)、聚萘二甲酸乙二酯薄膜(PEN薄膜)、聚對苯二甲酸丁二酯薄膜(PBT薄膜)等。
聚烯烴薄膜,可使用二軸延伸聚丙烯薄膜(OPP薄膜)等之聚 丙烯薄膜、聚乙烯薄膜等。
最外層2之厚度並無限定,通常在10~50μm之範圍。
屏蔽層3,通常是由金屬箔所成。金屬箔,可使用鋁(包含其合金)箔、銅(包含其合金)箔、鎳(包含其合金)箔、鈦(包含其合金)箔、不銹鋼箔等,特別適宜使用鋁箔。此外,金屬箔亦可為於其一面或兩面形成有化成皮膜等之防腐蝕處理層(未圖示)者。
屏蔽層3之厚度並無限定,通常在5~50μm之範圍,特別是在10~40μm之範圍為理想。
密封層4,是由聚丙烯薄膜、聚乙烯薄膜等所成。聚丙烯薄膜可使用無延伸聚丙烯薄膜(CPP薄膜)等。聚乙烯薄膜可使用直鏈狀低密度聚乙烯薄膜(LLDPE薄膜)等。
外側接著劑層5之接著劑,只要是可接著最外層2及屏蔽層3者則並無限定,該接著劑特別以使用二液硬化型胺甲酸乙酯系接著劑為理想。其理由在於,二液硬化型胺甲酸乙酯系接著劑具有高耐水性、高耐候性等。
外側接著劑層5,例如藉由下述方法形成:藉由指定之塗佈方法將外側接著劑層5之接著劑塗佈至作為與最外層2接著的層之屏蔽層3(詳細而言為屏蔽層3之面向最外層2側的面)上。
外側接著劑層5之接著劑之塗佈方法(即外側接著劑層5之形成方法),可使用凹版塗佈法、噴霧塗佈法、刮刀塗佈法等,特別以使用凹版塗佈法為理想。其理由如下所述。
亦即,凹版塗佈法中,通常是使用表面施有指定網孔數及深 度之雕刻之凹版輥進行模式(pattern)塗佈。因此,藉由以凹版塗佈法將接著劑塗佈至屏蔽層3上,如圖1所示,外側接著劑層5之面向最外層2側的面5a會形成為規則性排列之細微的凹凸狀。並且,若將最外層2接著於此面5a,則形成於此面5a之細微的凹凸形狀會反映至最外層2之表面2a。其結果,形成於此面5a之凹凸處與形成於最外層之表面2a之凹凸處一致。藉此,可使作為最外層2的表面2a之外裝材1的表面確實地實現指定之表面性狀。
內側接著劑層6之接著劑,只要是可接著屏蔽層3及密封層4者則並無限定,該接著劑可使用熱硬化型酸變性聚丙烯接著劑等。
內側接著劑層6之接著劑之塗佈方法(即內側接著劑層6之形成方法)並無限定,接著劑之塗佈方法,可使用上述之凹版塗佈法、噴霧塗佈法、刮刀塗佈法等。
本實施型態中,外裝材1在最外層2之表面2a之表面性狀中必須滿足第1要件:算術平均高度Sa之範圍為0.03~0.20μm;以及第2要件:當將由Sa的基準面+0.1μm之高度位置的截面積為7500μm2以上之凸部定義為山8(參照圖2)時,山8之數量範圍為每1mm2 5~30個。又,表面性狀係依據ISO 25178而測定。
藉由滿足第1及第2要件,最外層2之表面2a在具有高滑動性的同時,由於與黏著帶之接觸面積較大,故在最外層2之表面2a與黏著帶之密著性方面亦具有高密著性。因此,能以黏著帶牢固地固定鋰離子電池的位置。
進一步,當將山8中由Sa的基準面+0.1μm之高度位置之截面的重心位置(圖心位置)定義為山8之重心位置C(參照圖3)時,外裝材1,理想 為滿足第3要件:存在於1mm2中相互鄰近之山8之重心位置C間的距離範圍皆為150~700μm。
藉由滿足第3要件,除了可確實地提高最外層2之表面2a之滑動性,由於可確實地增大與黏著帶之接觸面積,故在最外層2之表面2a與黏著帶之密著性方面亦可確實地提高。因此,能以黏著帶確實地牢固地固定鋰離子電池的位置。
在此,針對第2及第3要件參照圖2及3說明如下。
圖2為顯示最外層2的表面2a之表面凹凸像中由Sa的基準面+0.1μm之高度的等高線之概略圖。
第2要件中,Sa的基準面係指最外層2表面2a之測定區域之平均高度的平面。由基準面+0.1μm之高度的截面積係指由基準面+0.1μm之高度之等高線所包圍的面積。並且,此面積為7500μm2以上之凸部被定義為山8。此外,規定山8之數量之「1mm2」,係指測定區域中相互正交之X方向1mm及Y方向1mm之正方形區域S。於圖2之情形,山8之數量為8個。
又,關於橫跨1mm2正方形區域S之外周邊界線10而存在之山,將重心位置C存在於外周邊界線10的內側或存在於外周境界線10上的山計入存在於1mm2之山之數量,而重心位置C存在於外周邊界線10的外側的山則不計入存在於1mm2之山之數量。
圖3為說明圖2所示之概略圖中相互鄰近之山8之重心位置C間的距離之圖。
於同圖所示之山8之分布狀態的情形下,滿足第3要件係指對於測定區域中存在於1mm2正方形區域S之所有山8(即8個山8),其相互鄰近 之山8之重心位置C間的距離d1~d11範圍皆為150~700μm。
以上說明本發明之實施型態,惟本發明並非限定於上述實施型態者,只要在不脫離本發明宗旨之範圍內可進行各種變更。
此外,本發明之蓄電裝置用外裝材,並不限定用於鋰離子電池,亦可用於其他蓄電裝置,例如可用於鋰離子電容器,亦可用於電雙層電容器。
本發明之具體實施例及比較例如以下所示。惟,本發明並非限定於下述實施例者。
<實施例1>
準備作為形成最外層2之薄膜之二軸延伸6尼龍薄膜(厚度25μm)、作為形成屏蔽層3之金屬箔之鋁箔(厚度35μm)、以及作為形成密封層4之薄膜之無延伸聚丙烯薄膜(厚度30μm)。
在鋁箔(屏蔽層3)的兩面分別形成化成皮膜。其形成方法如下所述。亦即,在鋁箔的兩面分別塗佈包含磷酸、聚丙烯酸(丙烯酸系樹脂)、鉻(III)鹽化合物、水及醇類之化成處理液,並在180℃下進行乾燥,藉此形成化成皮膜。化成皮膜之鉻之附著量為10mg/m2。
其次,在鋁箔的其中一面以凹版塗佈法塗佈作為外側接著劑層5之接著劑之二液硬化型胺甲酸乙酯系接著劑,並進行乾燥。藉此,在鋁箔的其中一面形成外側接著劑層5。接著劑之乾燥後之塗佈量為3.5g/m2。
上述之凹版塗佈法中,使用表面施有網孔數85及深度120μm 之格子型雕刻的凹版輥。
接著,以外側接著劑層5暫時接著(temporary adhesion)鋁箔與二軸延伸6尼龍薄膜(最外層2)。
其次,在鋁箔的另一面塗佈作為內側接著劑層6之接著劑之熱硬化型酸變性聚丙烯接著劑,並進行乾燥。藉此,在鋁箔的另一面形成內側接著劑層6。接著劑之乾燥後之塗佈量為2.5g/m2。
接著,以內側接著劑層6暫時接著(temporary adhesion)鋁箔與無延伸聚丙烯薄膜(密封層4)。藉此,得到以積層狀具備由二軸延伸6尼龍薄膜所成之最外層2、由鋁箔所成之屏蔽層3、及由無延伸聚丙烯薄膜所成之密封層4之外裝材材料。
其次,藉由將外裝材材料在靜置於40℃之環境下9日之條件下進行加熱老化處理,使外側接著劑層5及內側接著劑層6同時硬化。藉此,在以外側接著劑層5真正接著最外層2與屏蔽層3的同時,以內側接著劑層6真正接著屏蔽層3與密封層4。
藉由以上方法得到鋰離子電池用外裝材1。
<實施例2~7、比較例1~4>
對最外層(二軸延伸6尼龍薄膜)2之厚度、凹版輥表面所施有之網孔數及深度進行各種變更,並以與上述實施例1相同的方式得到外裝材1。
對於上述之實施例1~7及比較例1~4之各外裝材1,測定最外層2之表面2a之表面性狀,並且查驗最外層2之表面2a與黏著帶之密著性,並且為了評價最外層2之表面2a之滑動性測定最外層2之表面2a之動摩擦係數。其結果整理示於表1。
表1中「最外層」的「材質」欄中,「Ny」係指二軸延伸6尼龍薄膜。
表面性狀之測定、與黏著帶之密著性之評價、以及動摩擦係數(滑動性)之測定分別係以如下之方式進行。
<<表面性狀>>
對於外裝材1之最外層2之表面2a依據ISO 25178測定表面性狀,在測定算術平均高度Sa的同時,測定每1mm2之山8之數量、以及存在於1mm2中相互鄰近之山8之重心位置C間的距離。此時之測定條件及測定方法如下所述。
自外裝材1切出縱10mm×橫10mm的正方形試料。對於此試料之表面使用掃描型白光干涉顯微鏡(日立先端科技公司製「VS1330」)在任意處測定表面性狀。用於此測定之透鏡為雙光束干涉物鏡5×、波長濾波器為520nm。
表1中「最小距離dmin」欄及「最大距離dmax」欄之數值,分別代表存在於1mm2中相互鄰近之山8之重心位置C間的距離之最小距離dmin及最大距離dmax。
<<與黏著帶之密著性>>
以下述之條件及方法查驗最外層2之表面2a與黏著帶之密著性。
自外裝材1切出寬度15mm×長度150mm之試驗片。在此試驗片之表面沿其長度方向貼上黏著力13N/cm之黏著帶(tesa 70415)。黏著帶之寬度為5mm,其長度為80mm以上。接著,在此黏著帶上來回運行重量2kgf之手動輥(hand roll)5次,其後在常溫下靜置1小時。
其次,使用島津製作所製strograph(AGS-5kNX)作為拉伸試 驗機,在以其一側之夾頭夾住並固定試驗片之端部的同時,以另一側之夾頭抓住黏著帶之端部。接著,依據JIS K6854-3(1999)測定以300mm/min之剝離速度進行180°剝離時之剝離強度,將此測定值穩定時的值視為最外層2之表面2a與黏著帶之密著力(其單位:N/5mm)。
接著,對於最外層2之表面2a與黏著帶之密著性之評價基準,將與黏著帶之密著力為6N/5mm以上之情形評價為「◎(非常高)」,將5N/5mm以上未滿6N/5mm之情形評價為「○(高)」,以及將未滿5N/5mm之情形評價為「×(低)」。
<<動摩擦係數(滑動性)>>
為了評價最外層2之表面2a之滑動性,依據JIS K7125(1999)測定最外層2之表面2a之動摩擦係數。
如表1所示,實施例1~7之外裝材1之最外層2之表面2a的動摩擦係數小、滑動性良好。進一步,實施例1~7之外裝材1之最外層2之表面2a與黏著帶之密著性高,特別是實施例1~6之外裝材1之最外層2之表面2a與黏著帶之密著性非常高。
本案係依據於2018年7月20日提出申請之日本專利申請案特願2018-137069號主張優先權者,其所揭露之內容直接構成本案之一部分。
須認識到,此說明書所使用之用語及表現,係用以進行說明,並非用以限定解釋,且並非排除在此所示且所述之特徵事項之任何均等物者,而係容許於此發明所請之範圍內進行各種變形者。
在此雖記載了本發明之圖示實施型態,惟本發明並非限定於在此所記載之實施型態者,而係包含具有基於此公開所謂所屬技術領域中 具有通常知識者所能認知的均等要素、修正、刪除、組合(例如:跨越各種實施型態之特徵之組合)、改良及/或變更之所有實施型態者。
本發明可用於蓄電裝置(例如:鋰離子電池、鋰離子電容器、電雙層電容器)用外裝材。
1‧‧‧外裝材
2‧‧‧最外層
2a‧‧‧最外層之表面
3‧‧‧屏蔽層
4‧‧‧密封層
5‧‧‧外側接著劑層
5a‧‧‧外側接著劑層面向最外層側的面
6‧‧‧內側接著劑層
Claims (6)
- 一種蓄電裝置用外裝材,其以積層狀具備最外層、密封層、及配置於前述兩層間之屏蔽層,其特徵係:前述最外層,是由選自聚醯胺薄膜、聚酯薄膜及聚烯烴薄膜所成群中至少一種所成;前述最外層之表面之表面性狀中,算術平均高度Sa之範圍為0.03~0.20μm,當由前述Sa的基準面+0.1μm之高度位置的截面積為7500μm 2以上之凸部定義為山時,山之數量範圍為每1mm 2 5~30個。
- 如申請專利範圍第1項所記載之蓄電裝置用外裝材,其中,當前述山中由前述基準面+0.1μm之高度位置之截面的重心位置定義為前述山之重心位置時,存在於1mm 2中相互鄰近之前述山之重心位置間的距離範圍皆為150~700μm。
- 如申請專利範圍第1或2項所記載之蓄電裝置用外裝材,其中,前述最外層及前述屏蔽層,是以配置於此兩層間之接著劑層接著,且前述接著劑層之面向前述最外層側的面形成為凹凸狀。
- 如申請專利範圍第3項所記載之蓄電裝置用外裝材,其中,形成於前述接著劑層之面向前述最外層側的面之凹凸處,與形成於前述最外層之表面之凹凸處大略一致。
- 一種蓄電裝置用外裝材之製造方法,其是如申請專利範圍第3項所記載之蓄電裝置用外裝材之製造方法,其特徵係: 藉由凹版塗佈法將外裝材中配置於最外層與屏蔽層之間之接著劑層之接著劑塗佈至屏蔽層上。
- 一種蓄電裝置,其特徵係以如申請專利範圍第1至4項中任一項所記載之蓄電裝置用外裝材包裝蓄電裝置內容物。
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