TW201637266A - 微多孔膜及其製造方法、蓄電裝置、鋰離子電池以及電容器 - Google Patents
微多孔膜及其製造方法、蓄電裝置、鋰離子電池以及電容器 Download PDFInfo
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- 239000012982 microporous membrane Substances 0.000 title claims abstract description 46
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 14
- 239000003990 capacitor Substances 0.000 title claims description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims description 5
- 229910001416 lithium ion Inorganic materials 0.000 title claims description 5
- 229920000642 polymer Polymers 0.000 claims abstract description 27
- -1 polypropylene Polymers 0.000 claims abstract description 26
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- 229920001155 polypropylene Polymers 0.000 claims abstract description 25
- 239000000155 melt Substances 0.000 claims abstract description 14
- 238000002844 melting Methods 0.000 claims description 14
- 230000008018 melting Effects 0.000 claims description 14
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- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 5
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- 238000010438 heat treatment Methods 0.000 claims description 4
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- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
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- 239000002904 solvent Substances 0.000 description 2
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- 239000000057 synthetic resin Substances 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
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- 229920005653 propylene-ethylene copolymer Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
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Abstract
本發明提供一種作為電池隔片材料而有用的高空孔率的聚丙烯系樹脂製微多孔膜。本發明在於一種微多孔膜及其製造方法,所述微多孔膜包含依據JIS K6758且於230℃、荷重21.18 N下測定的熔體質量流動速率(MFR)為1.0 g/10 min以下的聚丙烯系聚合體,並且空孔率為50%以上。
Description
本發明是有關於一種包含聚丙烯系聚合體的微多孔膜、由其獲得的蓄電裝置、以及所述微多孔膜的製造方法。
作為電池或電容器等蓄電裝置的隔片,使用各種微多孔膜。對於隔片用微多孔膜,首先要求能夠隔離電極、具有離子傳導性的作為隔片的基本性能。聚烯烴系樹脂就耐化學品性高、可利用多種方法來進行多孔化的方面而言,作為電池隔片的材料而有用。而且,聚烯烴系樹脂由於在合成樹脂中比較價廉,故而聚烯烴製電池隔片亦有利於電池製造成本的削減。
聚烯烴系樹脂膜的多孔化方法大致劃分為濕式法與乾式法。濕式法中,將聚烯烴系樹脂與塑化劑、油、石蠟等的熔融混合物展開為膜狀。繼而,萃取出聚烯烴以外的成分,使該些成分所存在的部分空隙化。其結果為,聚烯烴系樹脂經成形加工為微多孔膜。乾式法中為如下方法:藉由使不包含塑化劑、油、石蠟等成分或溶劑的以聚烯烴系樹脂作為主體的原料進行延伸,而將聚烯烴系樹脂成形加工為微多孔膜。乾式法已知:使聚烯烴系樹脂中的片晶(lamella)結構的間隙中產生空隙的方法、以及使添加於原料中的無機添加劑與聚烯烴系樹脂的界面產生空隙的方法。
例如於專利文獻1、專利文獻2、專利文獻3中記載有:使聚烯烴系樹脂多孔化來製造空孔率高的微多孔膜;以及使用所獲得的微多孔膜作為電池隔片。
專利文獻1中記載有:利用濕式法,將包含聚烯烴系樹脂與共軛二烯聚合物的混合物的原料加工為具有所需空孔率的微多孔膜。
專利文獻2中記載有:藉由利用乾式法,將聚丙烯與聚乙烯的混合物以兩個階段進行延伸,而加工成具有所需空孔率的微多孔膜。
專利文獻3中記載有:藉由利用乾式法,將於聚烯烴中調配有低分子量物質的混合物以兩個階段進行延伸,而加工為具有所需空孔率的微多孔膜。
然而,作為合成樹脂製微多孔膜的製造方法,由於不使用溶劑的乾式法於成本方面有利,故而必須僅可能減少所使用的樹脂的種類或添加物的種類來實現低成本化,因此所述專利文獻1、專利文獻2、專利文獻3中記載的微多孔膜及其製造方法存在問題點。低成本、空孔率高、且包含聚烯烴系樹脂的微多孔膜依然存在改善的餘地。 [現有技術文獻] [專利文獻]
[專利文獻1]日本專利特開2004-352834號公報 [專利文獻2]日本專利特開2008-248231號公報 [專利文獻3]日本專利特開平8-20660號公報
[發明所欲解決之課題] 因此,本發明的發明者們為了將廉價的聚丙烯系樹脂不與其他樹脂摻合而用作原料,利用乾式法來製造具有良好空孔率的微多孔膜,而進行銳意研究。
[解決課題之手段] 其結果為,使用具有特定的熔體質量流動速率的聚丙烯系樹脂作為原料,利用乾式法而成功製造具有高空孔率的微多孔膜。
即,本發明為以下者。
(發明1)一種微多孔膜,其包含熔體質量流動速率(MFR(melt mass flow rate),以依據JIS K6758(230℃、21.18 N)的條件來測定)為1.0 g/10 min以下的聚丙烯系聚合體,且空孔率為50%以上。
(發明2)發明1的微多孔膜,其中空孔率在50%~60%的範圍內。
(發明3)發明1或發明2的微多孔膜,其中通氣度為200 sec/100 mL以上。
(發明4)發明1~發明3中任一項的微多孔膜,其中通氣度在200 sec/100 mL~300 sec/100 mL的範圍內。
(發明5)發明1~發明4中任一項的微多孔膜,其中聚丙烯系聚合體為丙烯主體的聚合體,其熔點在150℃~170℃的範圍內,熔體質量流動速率(MFR,以依據JIS K6758(230℃、21.18 N)的條件來測定)為1.0 g/10 min以下,並且所述聚合體可任意地包含選自乙烯、碳數4~8的α-烯烴中的至少一種。
(發明6)發明1~發明5中任一項的微多孔膜,其用於蓄電裝置的隔片。
(發明7)發明6的微多孔膜,其中蓄電裝置為鋰離子電池。
(發明8)發明6的微多孔膜,其中蓄電裝置為電容器。
(發明9)一種蓄電裝置,其包括發明6的微多孔膜。
(發明10)一種鋰離子電池,其包括發明7的微多孔膜。
(發明11)一種電容器,其包括發明8的微多孔膜。
(發明12)發明1~發明11中任一項的微多孔膜的製造方法,其包含以下的步驟: (步驟1)將依據JIS K6758且於230℃、荷重21.18 N下測定的熔體質量流動速率(MFR)為1.0 g/10 min以下的聚丙烯系聚合體進行擠出成形而製成原坯膜的步驟; (步驟2)對步驟1中獲得的原坯膜進行熱處理的步驟; (步驟3)將步驟2中獲得的熱處理後的原坯膜於-5℃~45℃下,於長度方向上延伸至1.0倍~1.1倍的步驟; (步驟4)於較聚丙烯系聚合體的熔點低5℃~65℃的溫度下,將結束了步驟3的延伸膜於長度方向上延伸至1.5倍~4.0倍的步驟;以及 (步驟5)於加熱下,以長度成為0.7倍~1.0倍的方式使步驟4中獲得的溫延伸後的膜鬆弛的步驟。 [發明的效果]
本發明的微多孔膜首先具有50%以上,較佳為50%~60%的高空孔率。這於使用本發明的微多孔膜作為隔片材料的情況下可期待高的離子導電性。
而且,本發明的微多孔膜具有200 sec/100 mL以上,較佳為200 sec/mL~300 sec/mL的通氣度。通常,微多孔膜的每單位表面面積的孔的數量反映在空孔率上,微多孔膜的微孔的平均大小反映在通氣度上。就該意義而言,本發明的空孔率與通氣度的平衡可預計於本發明的微多孔膜表面形成大量比較小的微孔。由此,對於本發明的微多孔膜可期待比較穩定且均勻的物質透過性。
本發明的微多孔膜包含熔體質量流動速率(MFR,以依據JIS K6758(230℃、21.18 N)的條件來測定)為1.0 g/10 min以下的聚丙烯系聚合體,且空孔率為50%以上。
(微多孔膜的原料) 本發明的微多孔膜的原料為聚丙烯系聚合體,將丙烯的均聚物或共聚單體進行共聚合而成的共聚物與其相當。本發明中使用的聚丙烯系聚合體較佳為結晶性比較高、熔點在150℃~170℃的範圍內者,尤佳為熔點在155℃~168℃的範圍內者。所述共聚單體通常為選自乙烯及碳數4~8的α-烯烴中的至少一種。另外,亦可為與該些共聚單體一併,將2-甲基丙烯、3-甲基-1-丁烯、4-甲基-1-戊烯等碳數4~8的分支烯烴類、苯乙烯類、二烯類進行共聚合而成者。
只要微多孔膜顯示出所需的性質,則所述共聚單體的含量可在任意的範圍內。較佳為相對於作為提供高結晶性聚丙烯系聚合體的範圍的聚合體100重量份,以5重量份以下,特別是2重量份以下為宜。
另外,所述聚丙烯系聚合體的熔體質量流動速率(MFR,以依據JIS K6758(230℃、21.18 N)的條件來測定)為1.0 g/10 min以下,較佳為0.2 g/10 min~0.6 g/10 min。
本發明的微多孔膜的原料中,可調配結晶核劑或填充劑等添加劑。添加劑的種類或量若為不損及多孔性的範圍,則無限制。
(微多孔膜的製造方法) 本發明的微多孔膜是使用所述的原料,利用所謂的乾式法來製造。本發明的微多孔膜的製造方法包含以下的步驟1~步驟5。
(步驟1:製膜步驟) 將原料擠出成形而製成原坯膜的步驟。將依據JIS K6758且於230℃、荷重21.18 N下測定的熔體質量流動速率(MFR)為1.0 g/10 min以下的聚丙烯系聚合體供給至擠出機中,將聚丙烯系聚合體於其熔點以上的溫度下進行熔融混練,而自安裝於擠出機的前端的模具中擠出聚丙烯系聚合體膜。所使用的擠出機並無限定。擠出機例如可使用:單軸擠出機、雙軸擠出機、串列型擠出機的任一者。所使用的模具若為用於膜成形者,則可使用任一者。模具例如可使用各種T型模具。原坯膜的厚度或形狀並無特別限定。較佳為模唇間距(dies lip clearance)與原坯膜厚度的比(牽伸比)為100以上,尤佳為150以上。較佳為原坯膜的厚度為10 μm~200 μm,尤佳為15 μm~100 μm。
(步驟2:熱處理步驟) 對結束了步驟1的原坯膜進行熱處理的步驟。於較聚丙烯系聚合體的熔點低5℃~65℃,較佳為低10℃~25℃的溫度下,對原坯膜施加長度方向的一定的張力。張力較佳為原坯膜的長度成為超過1.0倍且為1.1倍以下的大小。
(步驟3:冷延伸步驟) 將結束了步驟2的熱處理後的原坯膜於比較低的溫度下進行延伸的步驟。延伸溫度為-5℃~45℃,較佳為5℃~30℃。延伸倍率於長度方向上為1.0~1.1,較佳為1.00~1.08,尤佳為1.02以上且小於1.05。其中,延伸倍率大於1.0倍。延伸方法並無限制。可使用輥延伸法、拉幅機延伸法等公知的方法。延伸的階段數可任意地設定。可為一階段延伸,亦可經過多個輥而進行兩階段以上的延伸。於冷延伸步驟中,構成原坯膜的聚丙烯系聚合體的分子配向。其結果為,獲得包括分子鏈稠密的片晶部、以及片晶間的分子鏈疏散的區域(裂紋)的延伸膜。
(步驟4:溫延伸步驟) 將結束了步驟3的延伸膜於比較高的溫度下進行延伸的步驟。延伸溫度為較聚丙烯系聚合體的熔點低5℃~65℃的溫度,較佳為較聚丙烯系聚合體的熔點低10℃~45℃的溫度。延伸倍率於長度方向上為1.5倍~4.5倍,較佳為2.0倍~4.0倍。延伸方法並無限制。可使用輥延伸法、拉幅機延伸法等公知的方法。延伸的階段數可任意地設定。可為一階段延伸,亦可經過多個輥而進行兩階段以上的延伸。於溫延伸步驟中,步驟3中產生的裂紋延長而產生空孔。
(步驟5:鬆弛步驟) 為了防止結束了步驟4的溫延伸後的膜的收縮而使膜鬆弛的步驟。鬆弛溫度為較溫延伸的溫度稍高的溫度,通常為高0℃~20℃的溫度。鬆弛的程度是以結束了步驟4的延伸膜的長度最終成為0.7倍~1.0倍的方式進行調整。
本發明的微多孔膜所具有的「空孔率」及「通氣度」是於以下的條件下進行測定。
(空孔率) 對於寬度50 mm×長度120 mm的微多孔膜切片,利用以下的計算式來算出的值。 空孔率(%)=[1-(切片重量)/(切片面積×樹脂密度×切片厚度)]×100
(通氣度) 依據JIS P8117,藉由室溫為23℃±2℃、濕度為50%±5%的環境中的哥雷試驗(Gurley test)而求出的通氣度。
本發明的微多孔膜的空孔率為50%以上,較佳為在50%~60%的範圍內。本發明的微多孔膜的通氣度為200 sec/100 mL以上,較佳為在200 sec/100 mL~300 sec/100 mL的範圍內。 [實施例]
(實施例1) (原料)作為微多孔膜的原料,使用依據JIS K6758(230℃、21.18 N)來測定的熔體質量流動速率(MFR)為0.5 g/10 min、熔點為165℃的丙烯均聚物。(步驟1)利用單軸擠出機,將熔融混練的原料以牽伸比159自T字模中擠出,製造厚度為22 μm的原坯膜。(步驟2)繼而,將原坯膜於150℃下進行熱處理。(步驟3)於30℃下,將原坯膜於長度方向上冷延伸至1.03倍。(步驟4)於145℃下,將所獲得的延伸膜於長度方向上溫延伸至3.0倍。(步驟5)以所獲得的延伸膜的長度成為0.88倍的方式於150℃下使其鬆弛。如此獲得最終厚度為20 μm的本發明的微多孔膜。利用所述方法來測定所獲得的微多孔膜的空孔率及通氣度,將其結果與製造條件一併示於表1中。此外,通氣度的測定中,使用東洋精機製作所公司製造的通氣度計(哥雷(Gurley)式透氣度測定儀(densometer))。
(實施例2) (原料)作為微多孔膜的原料,使用依據JIS K6758(230℃、21.18 N)來測定的熔體質量流動速率(MFR)為0.5 g/10 min、且熔點為165℃的丙烯均聚物。(步驟1)利用單軸擠出機,將熔融混練的原料以牽伸比159自T字模中擠出,製造厚度為22 μm的原坯膜。(步驟2)繼而,將原坯膜於150℃下進行熱處理。(步驟3)於30℃下,將原坯膜於長度方向上冷延伸至1.04倍。(步驟4)於145℃下,將所獲得的延伸膜於長度方向上溫延伸至3.0倍。(步驟5)以所獲得的延伸膜的長度成為0.88倍的方式於150℃下使其鬆弛。如此獲得最終厚度為20 μm的本發明的微多孔膜。將評價結果與製造條件一併示於表1中。
(比較例1) (原料)作為微多孔膜的原料,使用依據JIS K6758(230℃、21.18 N)來測定的熔體質量流動速率(MFR)為2.0 g/10 min、且熔點為165℃的丙烯均聚物。(步驟1)利用單軸擠出機,將熔融混練的原料以牽伸比159自T字模中擠出,製造厚度為22 μm的原坯膜。(步驟2)繼而,將原坯膜於150℃下進行熱處理。(步驟3)於30℃下,將原坯膜於長度方向上溫延伸至1.07倍。(步驟4)於145℃下,將所獲得的延伸膜於長度方向上溫延伸至3.2倍。(步驟5)以所獲得的延伸膜的長度成為0.88倍的方式於150℃下使其鬆弛。如此獲得最終厚度為20 μm的比較用的微多孔膜。將評價結果與製造條件一併示於表1中。
(比較例2) (原料)作為微多孔膜的原料,使用依據JIS K6758(230℃、21.18 N)來測定的熔體質量流動速率(MFR)為1.5 g/10 min、且熔點為158℃的丙烯-乙烯共聚物。(步驟1)利用單軸擠出機,將熔融混練的原料以牽伸比159自T字模中擠出,製造厚度為22 μm的原坯膜。(步驟2)繼而,將原坯膜於150℃下進行熱處理。(步驟3)於30℃下,將原坯膜於長度方向上冷延伸至1.04倍。(步驟4)於128℃下,將所獲得的延伸膜於長度方向上溫延伸至3.0倍。(步驟5)以所獲得的延伸膜的長度成為0.88倍的方式於150℃下使其鬆弛。如此獲得最終厚度為20 μm的比較用的微多孔膜。將評價結果與製造條件一併示於表1中。
[表1]
實施例1、實施例2中獲得的本發明的微多孔膜的空孔率顯示出54%的高值。與此相對,比較例1、比較例2的微多孔膜的空孔率未達到50%,缺乏作為電池隔片的實用性。就空孔率及通氣度的平衡來看,預測為:實施例1、實施例2與比較例1、比較例2相比,高密度地存在孔徑比較小的微孔。此種微孔形態亦反映在微多孔膜的每單位厚度的通氣度上。認為與比較例1、比較例2相比,實施例1、實施例2穩定地發揮比較高的離子電導性。 [產業上之可利用性]
本發明的微多孔膜包含具有充分的多孔性且不含特別的添加劑的原料。此種本發明的微多孔膜作為具有優異的離子電導性、且可以低成本來製造的電池隔片的材料而有用。
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Claims (12)
- 一種微多孔膜,其包含熔體質量流動速率(MFR,以依據JIS K6758(230℃、21.18 N)的條件來測定)為1.0 g/10 min以下的聚丙烯系聚合體,且空孔率為50%以上。
- 如申請專利範圍第1項所述的微多孔膜,其中空孔率在50%~60%的範圍內。
- 如申請專利範圍第1項或第2項所述的微多孔膜,其中通氣度為200 sec/100 mL以上。
- 如申請專利範圍第1項至第3項中任一項所述的微多孔膜,其中通氣度在200 sec/100 mL~300 sec/100 mL的範圍內。
- 如申請專利範圍第1項至第4項中任一項所述的微多孔膜,其中聚丙烯系聚合體為丙烯主體的聚合體,其熔點在150℃~170℃的範圍內,熔體質量流動速率(MFR,以依據JIS K6758(230℃、21.18 N)的條件來測定)為1.0 g/10 min以下,並且所述聚合體能夠任意地包含選自乙烯、碳數4~8的α-烯烴中的至少一種。
- 如申請專利範圍第1項至第5項中任一項所述的微多孔膜,其用於蓄電裝置的隔片。
- 如申請專利範圍第6項所述的微多孔膜,其中蓄電裝置為鋰離子電池。
- 如申請專利範圍第6項所述的微多孔膜,其中蓄電裝置為電容器。
- 一種蓄電裝置,其包括如申請專利範圍第6項所述的微多孔膜。
- 一種鋰離子電池,其包括如申請專利範圍第7項所述的微多孔膜。
- 一種電容器,其包括如申請專利範圍第8項所述的微多孔膜。
- 一種如申請專利範圍第1項至第11項中任一項所述的微多孔膜的製造方法,其包含以下的步驟: (步驟1)將依據JIS K6758且於230℃、荷重21.18 N下測定的熔體質量流動速率(MFR)為1.0 g/10 min以下的聚丙烯系聚合體擠出成形而製成原坯膜的步驟; (步驟2)對步驟1中獲得的原坯膜進行熱處理的步驟; (步驟3)將步驟2中獲得的熱處理後的原坯膜於-5℃~45℃下,於長度方向上延伸至1.0倍~1.1倍的步驟; (步驟4)於較聚丙烯系聚合體的熔點低5℃~65℃的溫度下,將結束了步驟3的延伸膜於長度方向上延伸至1.5倍~4.0倍的步驟;以及 (步驟5)於加熱下,以長度成為0.7倍~1.0倍的方式使步驟4中獲得的溫延伸後的膜鬆弛的步驟。
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