TWI553943B - 鋰離子電池用外裝材料及使用鋰離子電池用外裝材料之鋰離子電池的製造方法 - Google Patents
鋰離子電池用外裝材料及使用鋰離子電池用外裝材料之鋰離子電池的製造方法 Download PDFInfo
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- TWI553943B TWI553943B TW102116304A TW102116304A TWI553943B TW I553943 B TWI553943 B TW I553943B TW 102116304 A TW102116304 A TW 102116304A TW 102116304 A TW102116304 A TW 102116304A TW I553943 B TWI553943 B TW I553943B
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- Prior art keywords
- layer
- exterior material
- lithium ion
- base material
- ion battery
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Description
本發明係關於鋰離子電池用外裝材料及使用鋰離子電池用外裝材料之鋰離子電池的製造方法。
本案依據在2012年5月10日於日本提出申請之日本特願2012-108355號主張優先權,其內容援用於此。
二次電池已知有鎳氫、鉛蓄電池,而由於攜帶式機器的小型化與設置空間的限制等,二次電池必須要小型化。因此,能量密度高的鋰離子電池備受注目。就使用於鋰離子電池之外裝材料(以下簡稱為「外裝材料」)而言,過去係使用金屬製的罐子,但現在使用輕量且放熱性高,並可對應低成本之多層薄膜。
鋰離子電池之電解液,係由碳酸丙烯酯、碳酸乙烯酯、碳酸二甲酯、碳酸二乙酯、碳酸甲乙酯等非質子性溶劑與電解質所構成。而電解質之鋰鹽係使用LiPF6、LiBF4等鋰鹽。但是,這些鋰鹽會因水分進行水解反應而產生氫氟酸。氫氟酸會引起電池構件的金屬面
腐蝕,並引起由多層薄膜所構成之外裝材料的各層間之積層強度降低。
因此,在由多層薄膜所構成之外裝材料中,係於內部設置鋁箔層,以抑制水分自多層薄膜的表面進入。已知例如,依序積層具有耐熱性之基材層/第1接著層/鋁箔層/防止氫氟酸造成的腐蝕之抗腐蝕處理層/第2接著層/密封層而成的外裝材料。使用前述外裝材料之鋰離子電池被稱為鋁積層型之鋰離子電池。
作為鋁積層型之鋰離子電池,已知例如:於外裝材料的一部分藉由冷間成型形成凹部,於前述凹部內收容電池內容物(正極、隔板、負極、電解液等),把外裝材料的剩餘部分折疊起來,以熱封(heat seal)將邊緣部分封止起來的壓紋型(embossed type)鋰離子電池。而且近年來,為了提高能量密度之目的,也製造在貼合的2個外裝材料之雙方形成凹部,能收容更多電池內容物之鋰離子電池。
鋰離子電池的能量密度,隨著藉由冷間成型形成之凹部的加深而變高。但是,隨著形成之凹部變深,在成型時於外裝材料會變得容易產生針孔或破裂。因此,在外裝材料的基材層使用雙軸拉伸聚醯胺薄膜,進行金屬箔之保護。
此處,作為提升成型性的範例,提案於基材層使用一種薄膜,該薄膜於0°、45°、90°、135°等4方向的拉伸試驗中,到破裂為止的拉伸強度為150MPa,且前述4方向的伸展為80%以上(例如參照專利文獻1)。
專利文獻1 日本專利第3567230號公報
然而,專利文獻1的技術對於成型加工後的翹曲(warp)完全沒有考慮。因此在一邊拉伸外裝材料一邊成型加工時,有無法改善經過拉伸之基材層為了回到原本的狀態而產生的翹曲之問題。
本發明係為了解決上述課題而作,提供了在維持優良的成型性的同時,還能減少成型加工後的翹曲量之鋰離子電池外裝材料及使用鋰離子電池用外裝材料之鋰離子電池的製造方法。
為了解決上述課題,本發明提案以下態樣。
本發明之一態樣的鋰離子電池用外裝材料中,具備:基材層,與在前述基材層的一面依序積層之第1接著層、金屬箔層、抗腐蝕處理層、第2接著層、及密封層;且於下述拉伸試驗,相對於前述試料的長度,於前述基材層的試料之MD方向及TD方向中的任一方之第1方向的拉伸伸長率係50%以上小於80%,且在垂直於前述第1方向的第2方向之拉伸應力係150MPa以上230MPa以下。
在23℃、40%RH之環境下,保管前述試料24小時後,在23℃、40%RH之環境下,以前述試料的寬度15mm、標點間距離50mm、拉伸速度100mm/分鐘之條件,實施拉伸試驗,測定前述試料的拉伸伸長率及拉伸應力。
本發明之一態樣中,於基材層的拉伸試驗,MD方向及TD方向中的任一方之第1方向的拉伸伸長率若為50%以上,則在成型時,能防止拉伸外裝材料造成的基材層破裂。
又,拉伸伸長率若小於80%,則能維持基材層的強度,並能提升成型性。
此外,於拉伸試驗的另一方向(垂直於前述第1方向的第2方向)的拉伸應力若為150MPa以上230MPa以下,則能抑制成型加工後的外裝材料之收縮,並能減少外裝材料的翹曲量。
另外,本發明之一態樣的鋰離子電池用外裝材料中,前述基材層係由聚醯胺或聚酯所構成,前述基材層的厚度較佳為10μm以上40μm以下。
本發明之一態樣中,藉由將基材層的厚度設為10μm以上,而能提升外裝材料之成型性。
又,藉由將基材層的厚度設為40μm以下,因可抑制藉由基材層的成型加工拉伸之處的收縮率,故能維持成型加工後的外裝材料之形狀,並能減少外裝材料的翹曲量。
此外,本發明之一態樣的鋰離子電池用外裝材料中,前述基材層較佳為藉由逐次雙軸拉伸法拉伸之薄膜。
本發明之一態樣中,基材層因具有機械性質的各向異性,而可抑制成型加工後的外裝材料之收縮,並能減少外裝材料的翹曲量。
然後,在本發明之一態樣的使用鋰離子電池用外裝材料之鋰離子電池的製造方法中,其係以使相對於前述基材層的拉伸應力為150MPa以上350MPa以下的方向呈垂直方向之部位成為折疊部之方式(例如以讓成為折疊蓋部之部位,與成型加工區域的邊緣部重疊之方式),將前述外裝材料成型加工。
藉此,外裝材料能抑制成型加工後的外裝材料之收縮,並能減少外裝材料之翹曲量。
依照本發明之鋰離子電池用外裝材料,藉由維持基材層的柔軟性或強度,使外裝材料維持優良的成型性,並藉由抑制成型加工後的外裝材料之收縮,而能減少外裝材料的翹曲量。
1‧‧‧鋰離子電池用外裝材料
11‧‧‧基材層
12‧‧‧第1接著層
13‧‧‧金屬箔層
14‧‧‧抗腐蝕處理層
15‧‧‧第2接著層
16‧‧‧密封層
17‧‧‧成型加工區域
第1圖係以示意的方式表示本發明之鋰離子電池用外裝材料的結構之截面圖。
第2圖係以示意的方式表示本發明之鋰離子電池用外裝材料的成型加工區域之平面圖。
第3圖係自紙面底面側觀看第2圖時之截面圖。
以下參照第1圖說明本發明之實施形態。
如第1圖所示,本實施形態之鋰離子電池用外裝材料1(以下稱為「外裝材料1」),係在具有薄片形狀之基材層11的一面上,依序積層同樣各自具有薄片形狀之第1接著層12、金屬箔層13、抗腐蝕處理層14、第2接著層15及密封層16而成的積層體。外裝材料1的基材層11係最外層,密封層16係最內層。亦即,外裝材料1係將基材層11配置在電池的外側(外面),將密封層16配置在電池的內側(內面)來使用。
基材層11係發揮於製造鋰離子電池時的密封步驟賦予耐熱性,與抑制加工或流通時會產生的針孔之發生之功用。
基材層11由在下述拉伸試驗中,在MD方向及TD方向中的任一方之方向(第1方向)的拉伸伸長率係50%以上小於80%,且在另一方之方向(垂直於前述第1方向的第2方向)的拉伸應力係150MPa以上230MPa以下之樹脂薄膜所構成之層。
其中,基材層11較佳為在下述拉伸試驗中,讓TD方向的拉伸伸長率為50%以上小於80%,讓MD方向的拉伸應力為150MPa以上230MPa以下。
進一步,基材層11更佳為讓TD方向的拉伸伸長率為75%,讓MD方向的拉伸應力為200MPa以下。
此處,MD方向係機械方向(Machine Direction)的簡稱,且為製造基材層11時的流動方向。TD方向係橫向方向(Transverse Direction)的簡稱,且與MD方向垂直之方向。
(拉伸試驗)
在23℃、40%RH之環境下,保管前述基材層的試料24小時後,在23℃、40%RH之環境下,以試料寬度15mm、標點間距離50mm、拉伸速度100mm/分鐘的條件,實施前述試料的拉伸試驗,測定前述試料的拉伸伸長率及前述試料的拉伸應力。
基材層11為了進行薄、且銳利(sharp)的形狀之成型,較佳使用強度高、伸展大、且軟質的聚醯胺(耐綸)或聚酯之薄膜。進一步由穿刺強度、衝撃強度優良的點而言,較佳為雙軸拉伸耐綸(ONy)薄膜或雙軸拉伸聚對苯二甲酸乙二酯(PET)薄膜。
其中,更佳為成型性較優良的雙軸拉伸耐綸薄膜。
基材層11的厚度較佳為10~40μm,更佳為20μm~35μm。基材層11的厚度若為10μm以上,則成型性優良。基材層11的厚度若為40μm以下,基材層11之藉由成型加工所拉伸處的收縮率不會變得比較大,外裝材料1可維持成型加工後的形狀。
作為基材層11,從減少外裝材料1在成型加工後的翹曲量之觀點來看,較佳為以逐次雙軸拉伸法拉
伸之具有機械性質的各向異性之逐次雙軸拉伸耐綸薄膜。
第1接著層12係接著基材層11與金屬箔層13之層。作為構成第1接著層12之接著材料,較佳為使作為硬化劑之2官能以上的芳香族系或脂肪族系異氰酸酯化合物作用於聚酯多元醇、聚醚多元醇、丙烯酸多元醇等主劑之2液硬化型的胺基甲酸酯系接著劑。
前述胺基甲酸酯系接著劑係藉由在塗布後,例如於40℃進行4日以上之老化,進行主劑之羥基與硬化劑之異氰酸酯基的反應,而能牢固地接著。
就接著強度、加工性等點而言,或為了得到追隨性(為了即便在設置第1接著層12之構件變形、伸縮時也不會剝離,確實地在構件上形成第1接著層12),第1接著層12的厚度較佳為1~10μm,更佳為3~7μm。
作為金屬箔層13,可使用鋁、不銹鋼等各種金屬箔,從防潮性、延展性等加工性、成本面來看,較佳為鋁箔。鋁箔可使用一般的軟質鋁箔。其中,從耐針孔性、及成型時的延展性優良的點而言,較佳為含鐵的鋁箔。
含鐵的鋁箔(100質量%)中,鐵的含量較佳為0.1~9.0質量%,更佳為0.5~2.0質量%。鐵的含量若為0.1質量%以上,則外裝材料1的耐針孔性、延展性優良。鐵的含量若為9.0質量%以下,則外裝材料1的柔軟性優良。
金屬箔層13的厚度,從阻隔性、耐針孔性、加工性的點來看,較佳為9~200μm,更佳為15~100μm。
抗腐蝕處理層14係發揮抑制電解液或藉由電解液與水分之反應所產生的氫氟酸對金屬箔層13之腐蝕的功用。另外,還發揮提高金屬箔層13與第2接著層15之密著力的功用。
作為抗腐蝕處理層14,較佳為藉由塗布型、或浸漬型的耐酸性之抗腐蝕處理劑所形成之塗膜。前述塗膜對金屬箔層13的酸具優良的抗腐蝕效果。另外,由於藉由錨定(anchor)效果而使金屬箔層13與第2接著層15的密著力更為牢固,所以對電解液等的內容物,可得到優良的耐性。此外,抗腐蝕處理層14也可依需要的功能,追加至第1接著層12與金屬箔層13之間。
作為前述塗膜,可列舉出例如:藉由利用包含氧化鈰、磷酸鹽與各種熱硬化性樹脂之抗腐蝕處理劑之氧化鈰溶膠處理所形成之塗膜;藉由利用包含鉻酸鹽、磷酸鹽、氟化物與各種熱硬化性樹脂之抗腐蝕處理劑之鉻酸鹽處理所形成之塗膜等。
更且,抗腐蝕處理層14只要是能充分得到金屬箔層13的耐腐蝕性之塗膜,前述塗膜即無限定。例如也可為藉由磷酸鹽處理、水鋁石處理等所形成之塗膜。
抗腐蝕處理層14可為單層,也可為複數層。另外,抗腐蝕處理層14中也可添加矽烷系偶合劑等之添加劑。
抗腐蝕處理層14的厚度,從抗腐蝕功能、及作為錨定之功能的點來看,較佳為10nm~5μm,更佳為20~500nm。
第2接著層15係接著形成有抗腐蝕處理層14之金屬箔層13與密封層16之層。外裝材料1依照形成第2接著層15之接著成分,大致分為熱層合組成與乾式層合組成。
作為形成熱層合組成的第2接著層15之接著成分,較佳為以順丁烯二酸酐等酸將聚烯烴系樹脂接枝改質而成的酸改質聚烯烴系樹脂。酸改質聚烯烴系樹脂由於在無極性之聚烯烴系樹脂的一部分導入了極性基,故能與以聚烯烴系樹脂薄膜等所形成之無極性的密封層16,及具有極性之抗腐蝕處理層14雙方牢固地密著。此外,藉由使用酸改質聚烯烴系樹脂,對電解液等內容物之耐性提升,即使電池內部產生了氫氟酸,也容易防止因第2接著層15的劣化造成的抗腐蝕處理層14與密封層16之密著力降低。
第2接著層15所使用之酸改質聚烯烴系樹脂,可為1種,也可為2種以上。
就酸改質聚烯烴系樹脂所用之聚烯烴系樹脂而言,可列舉出例如:低密度、中密度、高密度之聚乙烯;乙烯-α烯烴共聚物;同元、嵌段或無規聚丙烯;丙烯-α烯烴共聚物等。此外,亦可使用在前述化合物中共聚合丙烯酸或甲基丙烯酸等極性分子而成之共聚物、交聯聚烯烴等聚合物等。
就將前述聚烯烴系樹脂改質之酸而言,可列舉出羧酸、環氧化合物、酸酐等,較佳為順丁烯二酸酐。
就構成具有熱層合組成的第2接著層15之接著成分而言,從即便浸透了電解液,也容易維持密封層16與金屬箔層13之密著力的點來看,較佳為將聚烯烴系樹脂以順丁烯二酸酐接枝改質而成的順丁烯二酸酐改質聚烯烴系樹脂,特佳為順丁烯二酸酐改質聚丙烯。
順丁烯二酸酐改質聚丙烯的順丁烯二酸酐之改質率(相對於順丁烯二酸酐改質聚丙烯的總質量,源自順丁烯二酸酐之部分的質量),較佳為0.1~20質量%,更佳為0.3~5質量%。
在具有熱層合組成之第2接著層15中,較佳含有苯乙烯系或烯烴系彈性體。藉此,容易抑制在冷間成型時於第2接著層15產生裂痕而使外裝材料白化,可期待藉由潤濕性之改善產生的抗腐蝕處理層14與密封層16之密著力的提升,藉由各向異性降低產生的第2接著層15之製膜性的提升等。這些彈性體較佳以奈米級(奈米尺寸)分散並相溶於酸改質聚烯烴系樹脂中。
具有熱層合組成之第2接著層15,可藉由擠出前述接著成分之裝置擠出而形成。
具有熱層合組成之第2接著層15的接著成分之熔體流動速率(MFR)在230℃、2.16kgf之條件下,較佳為4~30g/10分鐘。
具有熱層合組成之第2接著層15的厚度,較佳為2~50μm。
就具有乾式層合組成之第2接著層15的接著成分而言,可舉出例如:與在第1接著層12所舉出的化合物相同之2液硬化型的聚胺基甲酸酯系接著劑。
具有乾式層合組成之第2接著層15,因具有酯基及胺基甲酸酯基等水解性高的鍵結部位,故在要求更高的可靠度之用途,較佳為具有熱層合組成之第2接著層15。
密封層16係外裝材料1中,藉由熱封賦予密封性之層。
就密封層16而言,可舉出由順丁烯二酸酐等的酸對聚烯烴系樹脂、或聚烯烴系樹脂接枝改質而成的酸改質聚烯烴系樹脂所構成之樹脂薄膜。
就前述聚烯烴系樹脂而言,可列舉出例如:低密度、中密度、高密度的聚乙烯;乙烯-α烯烴共聚物;同元、嵌段、或無規聚丙烯;丙烯-α烯烴共聚物等。這些聚烯烴系樹脂可單獨使用1種,也可2種以上併用。
就酸改質聚烯烴系樹脂而言,可舉出例如:與在第2接著層15所舉出之化合物相同的化合物。
密封層16可為單層薄膜,也可為多層薄膜,視需要的功能選擇即可。例如,就賦予防潮性的點而言,可使用夾有乙烯-環狀烯烴共聚物或聚甲基戊烯等樹脂之多層薄膜。
此外,密封層16也可調配阻燃劑、滑劑、防結塊劑、抗氧化劑、光穩定劑、增黏劑等各種添加材料。
密封層16的厚度較佳為10~100μm,更佳為20~60μm。
外裝材料1可為藉由乾式層合將密封層16積層在第2接著層15上而成之外裝材料,而從提升接著性的點而言,第2接著層15較佳係由酸改質聚烯烴系樹脂所構成,並藉由包夾層合(sandwitch lamination)將密封層16積層在第2接著層15上。
以下說明外裝材料1之製造方法。但外裝材料1之製造方法不限定於以下方法。
就外裝材料1之製造方法而言,可舉出例如具有下述步驟(1)~(3)之方法。
步驟(1):在金屬箔層13上形成抗腐蝕處理層14之步驟。
步驟(2):隔著第1接著層12,將基材層11貼合在與金屬箔層13之形成有抗腐蝕處理層14之面的相反面上之步驟。
步驟(3):隔著第2接著層15,將密封層16貼合在金屬箔層13之形成有抗腐蝕處理層14之面上之步驟。
(步驟(1))
將抗腐蝕處理劑塗布在金屬箔層13的一面上,並乾燥,形成抗腐蝕處理層14。就抗腐蝕處理劑而言,可列舉出例如:前述氧化鈰溶膠處理用的抗腐蝕處理劑、鉻酸鹽處理用的抗腐蝕處理劑等。
抗腐蝕處理劑之塗布方法無特別限定,可採用凹版塗布、反向式(reverse)塗布、輥塗布、棒塗布等各種方法。
(步驟(2))
使用形成第1接著層12之接著劑,以乾式層合等方式,將基材層11貼合在與金屬箔層13的形成有抗腐蝕處理層14之面的相反面上。
於步驟(2),為了促進接著性,也可在室溫~100℃之範圍進行老化(養生)處理。
(步驟(3))
藉由擠出層合法,將第2接著層15形成在,以基材層11、第1接著層12、金屬箔層13及抗腐蝕處理層14之順序積層而成之積層體的抗腐蝕處理層14側上,且貼合形成密封層16之樹脂薄膜。密封層16之積層較佳藉由包夾層合進行。
經由以上說明之步驟(1)~(3),可得到外裝材料1。
其中,外裝材料1之製造方法的步驟順序,不限定於依前述(1)~(3)之順序實施之方法。也可例如在進行步驟(2)後進行步驟(1)。
以下,基於第2圖及第3圖說明使用本實施形態之外裝材料1的鋰離子電池之製造方法中,對外裝材料1之成型加工方法的一範例。
又,此處,說明在製造鋰離子電池之過程中,在從上部(厚度方向)觀看外裝材料1之情形,形成成形為矩形之凹部的成型加工區域17之成型加工方法。
即,此成型加工區域17係藉由例如讓具有矩形之壓力面的按壓構件,對外裝材料1的一部分,於外裝材料1的厚度方向按壓來形成。另外,藉由將按壓區域,即,成型加工區域17,配置在靠近裁切為片狀之外裝材料1的一側之部位(第1部位),能在成型加工後將另一側之部位(第2部位)折疊,並將第2部位作為蓋子來形成。
此外,作為成為此種折疊部位之處(線部位),相對於基材層11的拉伸應力為150MPa以上350MPa以下之方向,較佳呈垂直。
進行此種外裝材料之成型加工後,藉由對外裝材料1實施以下步驟,來製造鋰離子電池。
即,如上述步驟般形成凹部的成型加工區域17後,在前述凹部的內部放入正極、隔板及負極,將外裝材料1折疊,以讓密封層相對的方式重疊,將經過該重疊之外裝材料的外緣的二邊予以熱封。然後,藉由於真空狀態下,從剩下的外裝材料之一邊注入電解液,將剩下的外裝材料之一邊重疊,熱封並密封,而得到鋰離子電池。
又,製造本發明之鋰離子電池用外裝材料所適用之鋰離子電池之方法,不限定於上述方法。
依照上述之外裝材料1,在基材層11的拉伸試驗中,藉由讓基材層之試料的TD方向的拉伸伸長率為75%,能防止外裝材料1的拉伸過度或拉伸不足,並能提升外裝材料1的成型性。
此外,在基材層11的拉伸試驗中,藉由讓基材層之試料的MD方向的拉伸應力設為200MPa,可實現成型加工後的翹曲量之降低。
另外,藉由讓基材層11的厚度在20μm~35μm,在提升外裝材料1的成型性的同時,還能實現成型加工後的外裝材料1的翹曲量之降低。
此外,藉由將基材層11成為逐次雙軸拉伸耐綸薄膜,基材層11具有機械性質之各向異性,且可實現成型加工後的外裝材料1的翹曲量之降低。
因此,依據本實施形態的鋰離子電池之製造方法,藉由以使與基材層11的拉伸應力為150MPa以上350MPa以下之方向呈垂直方向為折疊部的方式,進行成型加工,能實現成型加工後的翹曲量之降低。
以下,依據實施例詳細說明本發明,但本發明不受以下記載限定。
以下表示本實施例所使用之材料。
(基材層11)
基材A-1:逐次雙軸拉伸Ny薄膜
基材A-2:逐次雙軸拉伸Ny薄膜
基材A-3:逐次雙軸拉伸Ny薄膜
基材A-4:管狀法雙軸拉伸Ny薄膜
(第1接著層12)
接著劑B-1:胺基甲酸酯系接著劑(商品名「A525/A50」,三井化學聚氨酯公司製)
(金屬箔層13)
金屬箔C-1:軟質鋁箔8079材(東洋鋁公司製,厚度40μm)
(抗腐蝕處理層14)
處理劑D-1:以氧化鈰、磷酸、丙烯酸系樹脂為主體之塗布型氧化鈰溶膠處理用處理劑。
(第2接著層15)
接著樹脂E-1:以順丁烯二酸酐接枝改質之聚丙烯系樹脂(商品名「ADMER」,三井化學公司製)
(密封層16)
薄膜F-1:無拉伸聚丙烯薄膜(厚度40μm)之作為內面之面經過電暈處理之薄膜。
將處理劑D-1塗布在作為金屬箔層13之金屬箔C-1的一面上,加以乾燥,形成抗腐蝕處理層14。接下來,藉由使用接著劑B-1的乾式層合法,將基材A-1~A-4中的任一者,貼合在與金屬箔層13的形成有抗腐蝕處理層14之面的相反面上,隔著第1接著層12將基材層11加以積層。然後,進行60℃、6天之老化。接下來,以擠出裝置將接著樹脂E-1擠出至所得到的積層體之形成有抗腐蝕處理層14之面上,形成第2接著層15,藉由將薄膜F-1貼合並包夾層合而形成密封層16。然後,藉由對所得到之積層體,以160℃、4kg/cm2、2m/分鐘之條件加熱壓接,製成外裝材料1。
對基材層11所使用之各薄膜,在23℃、40%RH之環境下,將基材層11的試料保管24小時後,在23℃、40%RH之環境下,進行拉伸試驗(試料寬度15mm、標點間距離50mm、拉伸速度100mm/分鐘),測定MD方向及TD方向的拉伸伸長率與拉伸應力。
將各例所得到之外裝材料,裁取為150mm×190mm之空白形狀(平面形狀),在23℃、40%RH的成型環境下,一邊改變成型深度,一邊加以冷間成型,評價成型性。
作為衝頭(punch),係使用形狀為100mm×150mm,衝頭圓角半徑(RCP)為1.5mm,衝頭肩角半徑(RP)為0.75mm、母模肩角半徑R(RD)為0.75mm之模具。評價基準係依據下述來執行。
「優」:外裝材料1沒有產生破裂、裂痕,且能進行成型深度7mm以上之拉深成型。
「良」:外裝材料1沒有產生破裂、裂痕,且能進行成型深度5mm以上小於7mm之拉深成型。
「不良」:在進行成型深度小於5mm之拉深成型時,外裝材料1產生破裂、裂痕。
對各例所得到之外裝材料,把於拉伸評價所得到之拉伸伸長率大之方向設為長邊,裁取120mm×260mm之空白形狀(平面形狀),在23℃、40%RH之成型環境下,取成型深度4mm,進行冷間成型。
成型區域係決定在離裁切為空白形狀之外裝材料的端部(裁切為平面形狀之外裝材料的外緣),與成型區域的外周之一邊,25mm遠之位置。於裁切為空白形狀之外裝材料(裁切為平面形狀之外裝材料)的一側之外緣附近(離外裝材料之邊緣的三邊,與成型區域之外周的三邊,25mm遠之位置),形成成型區域。
作為衝頭,係使用形狀為70mm×80mm,衝頭圓角半徑(RCP)為1.5mm,衝頭肩角半徑(RP)為0.75mm、母模肩角半徑R(RD)為0.75mm之模具。
將經過成型加工的外裝材料,以讓成型區域的基材層成為上部的方式,對平坦的基準面加以固定,測定自成型加工起60分鐘後,未成型之區域的端邊的翹曲量(自基準面的距離)。評價基準係依據下述評價翹曲量。
「優」:外裝材料的翹曲量小於50mm未滿。
「良」:外裝材料的翹曲量係50mm以上小於100mm。
「不良」:外裝材料翹曲量係100mm以上。
將成型性及翹曲之評價結果示於表1。
如表1所示,將基材層的TD方向的拉伸伸長率為75%且基材層的MD方向的拉伸應力為200MPa之逐次雙軸拉伸Ny薄膜使用於基材層之實施例1,確認外裝材料的翹曲量的降低。此外,實施例1所用之外裝材料也顯示優良的成型性。
另一方面,基材層的TD方向的伸長率為85%之比較例1所用的外裝材料,由於拉伸不足造成的薄膜強度降低,得不到充分的成型性。又,基材層的TD方向的伸長率為45%之比較例2所用的外裝材料,薄膜的柔軟性降低,且經過成型加工,外裝材料破裂。
另外,管狀法雙軸拉伸Ny薄膜之比較例3所用的外裝材料,在基材層的TD方向的拉伸伸長率大的同時,因能對外裝材料進行在MD方向及TD方向的方向性取得沒有偏差的平衡之充分的拉伸,關於成型性係顯示優良的結果。另一方面,關於外裝材料的翹曲量,因基材層的MD方向的拉伸應力係較大的235MPa,而成為不良之結果。
由以上可知,藉由於基材層使用基材層的TD方向的拉伸伸長率為75%且基材層的MD方向的拉伸應力為200MPa之逐次雙軸拉伸Ny薄膜時,在高度維持外裝材料的成型性的同時,還可降低外裝材料的翹曲量。
另外,不僅此條件,推測例如即使讓基材層的TD方向及MD方向中的任一方之方向(第1方向)的拉伸伸長率為75%,另一方之方向(第2方向)的拉伸應力為200MPa,也能得到與上述相同之效果。
此外,推測例如在讓基材層的TD方向及MD方向中的任一方之方向(第1方向)的拉伸伸長率為50%以上小於80%,另一方之方向(第2方向)的拉伸應力為150MPa以上230MPa以下之情形,也能得到與上述相同之效果。
1‧‧‧鋰離子電池用外裝材料
11‧‧‧基材層
12‧‧‧第1接著層
13‧‧‧金屬箔層
14‧‧‧抗腐蝕處理層
15‧‧‧第2接著層
16‧‧‧密封層
Claims (4)
- 一種鋰離子電池用外裝材料,其係具備:基材層,與於前述基材層的一面依序積層的第1接著層、金屬箔層、抗腐蝕處理層、第2接著層、及密封層;其中,於下述拉伸試驗,相對於前述試料的長度,前述基材層的試料之MD方向及TD方向的任一方之第1方向的拉伸伸長率係50%以上小於80%,而且,垂直於前述第1方向之第2方向的拉伸應力係150MPa以上230MPa以下;(拉伸試驗)在23℃、40%RH之環境下保管前述試料24小時後,在23℃、40%RH之環境下,以前述試料的寬度15mm、標點間距離50mm、拉伸速度100mm/分鐘之條件實施拉伸試驗,並測定前述試料之拉伸伸長率及拉伸應力。
- 如請求項1之鋰離子電池用外裝材料,其中前述基材層係由聚醯胺或聚酯所構成,且前述基材層的厚度為10μm以上40μm以下。
- 如請求項1或2之鋰離子電池用外裝材料,其中前述基材層係藉由逐次雙軸拉伸法所拉伸成的薄膜。
- 一種鋰離子電池之製造方法,其係使用如請求項1至3中任一項之鋰離子電池用外裝材料之鋰離子電池之製造方法, 其係將前述外裝材料成型加工,以使前述基材層中相對於前述基材層的拉伸應力為150MPa以上350MPa以下之方向呈垂直方向的部位成為折疊部。
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JP6331482B2 (ja) * | 2014-03-03 | 2018-05-30 | 大日本印刷株式会社 | 電池用包装材料 |
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JP6596912B2 (ja) * | 2015-05-13 | 2019-10-30 | 凸版印刷株式会社 | 蓄電デバイス用外装材及び蓄電デバイス |
WO2016111182A1 (ja) * | 2015-01-06 | 2016-07-14 | 凸版印刷株式会社 | 蓄電デバイス用外装材 |
CN107408645B (zh) | 2015-03-27 | 2020-09-01 | 大日本印刷株式会社 | 电池用包装材料、其制造方法和电池 |
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