TWI838942B - 鋰電池用鋁塑膜及其製造方法 - Google Patents
鋰電池用鋁塑膜及其製造方法 Download PDFInfo
- Publication number
- TWI838942B TWI838942B TW111142113A TW111142113A TWI838942B TW I838942 B TWI838942 B TW I838942B TW 111142113 A TW111142113 A TW 111142113A TW 111142113 A TW111142113 A TW 111142113A TW I838942 B TWI838942 B TW I838942B
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- Prior art keywords
- polyolefin
- rubber
- layer
- modified
- manufacturing
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 78
- 239000002985 plastic film Substances 0.000 title claims abstract description 50
- 229920006255 plastic film Polymers 0.000 title claims abstract description 50
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 26
- 229920000098 polyolefin Polymers 0.000 claims abstract description 102
- 229920000642 polymer Polymers 0.000 claims abstract description 57
- 239000011888 foil Substances 0.000 claims abstract description 52
- 238000004519 manufacturing process Methods 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 17
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000000576 coating method Methods 0.000 claims abstract description 8
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- 238000001035 drying Methods 0.000 claims abstract description 6
- 229920006124 polyolefin elastomer Polymers 0.000 claims description 71
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 42
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 42
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- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 33
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 33
- 229920001971 elastomer Polymers 0.000 claims description 29
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical group CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 claims description 28
- 229920005604 random copolymer Polymers 0.000 claims description 27
- 239000000178 monomer Substances 0.000 claims description 25
- 239000002245 particle Substances 0.000 claims description 21
- 239000012454 non-polar solvent Substances 0.000 claims description 20
- 239000002798 polar solvent Substances 0.000 claims description 20
- 239000004848 polyfunctional curative Substances 0.000 claims description 17
- 239000003607 modifier Substances 0.000 claims description 16
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 claims description 14
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- 239000000463 material Substances 0.000 claims description 12
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- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 6
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- 239000005977 Ethylene Substances 0.000 claims description 6
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 4
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- 229920001778 nylon Polymers 0.000 claims description 3
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- 239000000853 adhesive Substances 0.000 abstract 5
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- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 13
- 230000000694 effects Effects 0.000 description 11
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- 229920005672 polyolefin resin Polymers 0.000 description 9
- -1 polypropylene Polymers 0.000 description 8
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- 229920001155 polypropylene Polymers 0.000 description 7
- 238000005260 corrosion Methods 0.000 description 6
- LTVUCOSIZFEASK-MPXCPUAZSA-N (3ar,4s,7r,7as)-3a-methyl-3a,4,7,7a-tetrahydro-4,7-methano-2-benzofuran-1,3-dione Chemical compound C([C@H]1C=C2)[C@H]2[C@H]2[C@]1(C)C(=O)OC2=O LTVUCOSIZFEASK-MPXCPUAZSA-N 0.000 description 4
- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-UHFFFAOYSA-N 0.000 description 4
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 description 4
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- 230000009286 beneficial effect Effects 0.000 description 3
- IZJDCINIYIMFGX-UHFFFAOYSA-N benzo[f][2]benzofuran-1,3-dione Chemical compound C1=CC=C2C=C3C(=O)OC(=O)C3=CC2=C1 IZJDCINIYIMFGX-UHFFFAOYSA-N 0.000 description 3
- UHMARZNHEMRXQH-PHDIDXHHSA-N (3aR,7aR)-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1([C@H]2[C@H](C(=O)O1)CCC=C2)=O UHMARZNHEMRXQH-PHDIDXHHSA-N 0.000 description 2
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 2
- KMOUUZVZFBCRAM-UHFFFAOYSA-N 1,2,3,6-tetrahydrophthalic anhydride Chemical compound C1C=CCC2C(=O)OC(=O)C21 KMOUUZVZFBCRAM-UHFFFAOYSA-N 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
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- YKYONYBAUNKHLG-UHFFFAOYSA-N propyl acetate Chemical compound CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 2
- HMMBJOWWRLZEMI-UHFFFAOYSA-N 4,5,6,7-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CCCC2=C1C(=O)OC2=O HMMBJOWWRLZEMI-UHFFFAOYSA-N 0.000 description 1
- SJUPJFSPSDWZLL-UHFFFAOYSA-N C1(C=C/C(=O)O1)=O.C1(C=C/C(=O)O1)=O.C1(C=C/C(=O)O1)=O.C1(C=C/C(=O)O1)=O.C1(C=C/C(=O)O1)=O Chemical compound C1(C=C/C(=O)O1)=O.C1(C=C/C(=O)O1)=O.C1(C=C/C(=O)O1)=O.C1(C=C/C(=O)O1)=O.C1(C=C/C(=O)O1)=O SJUPJFSPSDWZLL-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
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- 239000000155 melt Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
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- 239000007787 solid Substances 0.000 description 1
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- 238000010998 test method Methods 0.000 description 1
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 1
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Abstract
本發明公開一種鋰電池用鋁塑膜及其製造方法。鋰電池用鋁塑膜的製造方法包括下列步驟:配製一聚烯烴膠,並將聚烯烴膠塗佈於一鋁箔層的其中一面上,接著,將一內側聚烯烴層設置於聚烯烴膠上,烘乾後鋁箔層與內側聚烯烴層之間形成一聚烯烴膠層。聚烯烴膠的成分包括一改質聚烯烴高分子與一硬化劑。改質聚烯烴高分子具有一改性基,改性基的結構中含有馬來酸酐。改質聚烯烴高分子的分子量為100000克/莫耳至200000克/莫耳。
Description
本發明涉及一種鋁塑膜及其製造方法,特別是涉及一種鋰電池用鋁塑膜及其製造方法。
根據封裝方式的不同,鋰電池可分為圓柱電池、方形電池與軟包電池。相較於其他種類,軟包電池具有安全性較佳以及重量較輕的優點。
在軟包電池中,鋁塑膜是製造軟包電池的重要材料。鋁塑膜包覆於電池電芯與電解液之外,以達到保護電池內容物的效果。鋁塑膜長時間接觸電解液,而需具備良好耐電解液的特性,另外,鋁塑膜還需具備可封裝的效果。
鋁塑膜的結構包括:一內側層、一外側層以及位於內側層與外側層之間的鋁箔層。內側層位於鋁塑膜的內側與電解液接觸,且可進行熱封,外側層位於鋁塑膜的外側與外界空氣接觸。
由於材料上的差異,鋁箔層與內側層之間可設置聚烯烴膠,鋁箔層與外側層之間可設置聚酯膠,以達到接合效果。
值得說明的是,在軟包電池中,內側層會與電解液接觸。因此,除了內側層要可耐受電解液之外,聚烯烴膠也要具備耐受電解液的條件。然而,為了達到良好的電解液耐受性,現有技術中的聚烯烴膠,具有較高的單價,導致軟包電池的價格高居不下。
因此,如何通過成分的改良,來降低聚烯烴膠的生產成本,並維持良好的電解液耐受性,已成為該項事業所欲解決的重要課題之一。
本發明所要解決的技術問題在於,針對現有技術的不足提供一種鋰電池用鋁塑膜及其製造方法。
為了解決上述的技術問題,本發明所採用的其中一技術方案是提供一種鋰電池用鋁塑膜的製造方法。鋰電池用鋁塑膜的製造方法包括:配製一聚烯烴膠,塗佈聚烯烴膠於一鋁箔層的其中一面上,設置一內側聚烯烴層於聚烯烴膠上,烘乾聚烯烴膠,以於鋁箔層與內側聚烯烴層之間形成一聚烯烴膠層。聚烯烴膠的成分包括一改質聚烯烴高分子與一硬化劑。所述改質聚烯烴高分子具有一改性基,所述改性基的結構中含有馬來酸酐。改質聚烯烴高分子的分子量為100000克/莫耳至200000克/莫耳。
於一些實施例中,改質聚烯烴高分子的酸價為0.1 mgKOH/g至10 mgKOH/g。
於一些實施例中,配製聚烯烴膠的步驟包括:於160°C至230°C的溫度下,熔融混合一聚烯烴膠粒與一改質劑,以形成一改質膠粒,使用改質膠粒配製成聚烯烴膠,改質膠粒的材料是改質聚烯烴高分子。
於一些實施例中,改質劑為是選自於由下列所構成的群組:馬來酸酐(Maleic Anhydride)、甲基四氫苯酐(Methyl tetrahydrophthalic anhydride,MTHPA)、轉位四氫苯酐(3,4,5,6-tetrahydrophthalic Anhydride)、四氫苯酐(1,2,3,6-tetrahydrophthalic Anhydride,THPA)、甲基六氫苯酐(Methylhexahydrophthalic Anhydride,MHHPA)、甲基納迪克酸酐(Methyl Nadic Anhydride,MNA)以及2,3-萘二甲酸酐(2,3-naphthalenedicarboxylic Anhydride)。
於一些實施例中,配製聚烯烴膠的步驟包括:添加一混合溶劑溶解一改質膠粒,再加入硬化劑,以形成聚烯烴膠。改質膠粒的材料是改質聚烯烴高分子,混合溶劑包含一非極性溶劑與一極性溶劑,非極性溶劑與極性溶劑的質量比例為4:1至3:2。
於一些實施例中,非極性溶劑為甲基環己烷,極性溶劑為甲乙酮、乙酸乙酯或其混合物。
於一些實施例中,改質聚烯烴高分子是一丙烯無規共聚物,丙烯無規共聚物是由丙烯單體聚合而成,以丙烯無規共聚物的總重為100重量百分比,丙烯單體的占比大於50重量百分比。
於一些實施例中,改質聚烯烴高分子是一丙烯無規共聚物,丙烯無規共聚物是由乙烯單體、丙烯單體與丁烯單體聚合而成。
於一些實施例中,改質聚烯烴高分子的熔點為60°C至90°C,改質聚烯烴高分子在120°C、負荷2.16公斤條件下測量的熔融指數(Melt Flow Index,MFI)為6克/10分鐘至30克/10分鐘。
於一些實施例中,鋰電池用鋁塑膜的製造方法進一步包括:塗佈一聚酯膠於鋁箔層的另外一面上,設置一外側層於聚酯膠上,外側層是尼龍層或聚酯層,烘乾聚酯膠,以於鋁箔層與外側層之間形成一聚酯膠層。
為了解決上述的技術問題,本發明所採用的另外一技術方案是提供一種鋰電池用鋁塑膜。鋰電池用鋁塑膜是由前述的鋰電池用鋁塑膜的製造方法製成。聚烯烴膠層與鋁箔層的耐電解液密著強度大於15 N/15mm,置於85°C的溫度下168小時後,聚烯烴膠層與鋁箔層的耐電解液密著強度大於12.5 N/15mm。
本發明的其中一有益效果在於,本發明所提供的鋰電池用鋁塑膜及其製造方法,其能通過“改質聚烯烴高分子具有改性基,改性基的結構中含有馬來酸酐”以及“改質聚烯烴高分子的分子量為100000克/莫耳至200000克/莫耳”的技術方案,以提升鋰電池用鋁塑膜的耐電解液密著強度。
為使能更進一步瞭解本發明的特徵及技術內容,請參閱以下有關本發明的詳細說明與圖式,然而所提供的圖式僅用於提供參考與說明,並非用來對本發明加以限制。
以下是通過特定的具體實施例來說明本發明所公開有關“鋰電池用鋁塑膜及其製造方法”的實施方式,本領域技術人員可由本說明書所公開的內容瞭解本發明的優點與效果。本發明可通過其他不同的具體實施例加以施行或應用,本說明書中的各項細節也可基於不同觀點與應用,在不悖離本發明的構思下進行各種修改與變更。另外,本發明的附圖僅為簡單示意說明,並非依實際尺寸的描繪,事先聲明。以下的實施方式將進一步詳細說明本發明的相關技術內容,但所公開的內容並非用以限制本發明的保護範圍。另外,本文中所使用的術語“或”,應視實際情況可能包括相關聯的列出項目中的任一個或者多個的組合。
為了降低製造成本的問題,本發明提供一種鋰電池用鋁塑膜及其製造方法,通過使用一種特殊的聚烯烴膠,結合鋁箔層與內側聚烯烴層。如此一來,本發明的鋁塑膜可具有優於市售鋁塑膜的耐電解液密著強度,即使長時間處於高溫環境,仍可保有良好的耐電解液密著強度。
請參閱圖1所示,本發明的鋰電池用鋁塑膜包括:一鋁箔層10、一內側聚烯烴層20以及一外側層30。
鋁箔層10位於內側聚烯烴層20與外側層30之間。鋁箔層10相對的兩個表面可經由防蝕處理,各自形成一防蝕處理層11、12,以達到保護鋁箔層10的效果。內側聚烯烴層20作為鋁塑膜的內表面,封裝後會與電解液接觸。外側層30作為鋁塑膜的外表面,封裝後會與外界空氣接觸。外側層30可以是一尼龍層或一聚酯層,但本發明不限於此。
由於材料上的差異,可於鋁箔層10與內側聚烯烴層20之間塗佈一聚烯烴膠,以形成一聚烯烴膠層40,達到黏合鋁箔層10與內側聚烯烴層20的效果。另可於鋁箔層10與外側層30之間塗佈一聚酯膠,以形成有一聚酯膠層50,達到黏合鋁箔層10與外側層30的效果。
於一示範實施例中,聚烯烴膠層40的厚度為2微米至10微米。較佳的,聚烯烴膠層40的厚度為3微米至5微米。
根據上述鋁塑膜的結構,聚烯烴膠除了要可黏合鋁箔層10與內側聚烯烴層20之外,還需具有一定程度的耐電解液密著強度,以維持內側聚烯烴層20與鋁箔層10之間的密著強度。
本發明的聚烯烴膠具有適當的熔點,不需以過高的溫度,即可進行加工。低溫加工的特色,可防止內側聚烯烴層20的物性受負面影響。並且,本發明的聚烯烴膠具有適當的黏度,可適用於塗佈製程。關於聚烯烴膠的具體配製方式,將於後敘述。
在本發明中,聚烯烴膠的成分包括一改質聚烯烴高分子與一硬化劑。硬化劑的種類可依需求選用。相較於100重量份的改質聚烯烴高分子,硬化劑的添加量為1重量份至10重量份。於一示範實施例中,硬化劑是聚異氰酸酯型硬化劑,例如:Desmodur
®ultra N 3300,但本發明不限於此。
改質聚烯烴高分子是一丙烯無規共聚物,也就是說,改質聚烯烴高分子是以丙烯單體與其他單體共同聚合而成。以丙烯無規共聚物的總重為100重量百分比,丙烯單體的占比大於50重量百分比。於一示範實施例中,丙烯無規共聚物是由乙烯單體、丙烯單體與丁烯單體聚合而成。
改質聚烯烴高分子中具有一改性基,改性基可接枝於改質聚烯烴高分子的主鏈或支鏈。於一示範實施例中,改性基是由馬來酸酐或馬來酸酐衍生物(結構中含有馬來酸酐的化合物)所形成。因此,改性基的結構中含有馬來酸酐。具體來說,改性基可以是由馬來酸酐、甲基四氫苯酐、轉位四氫苯酐、四氫苯酐、甲基六氫苯酐、甲基納迪克酸酐或2,3-萘二甲酸酐經接枝形成。
改質聚烯烴高分子的改性基,可降低丙烯無規共聚物的熔點。如此一來,可降低聚烯烴膠於貼合加工或其他加工程序中的操作溫度。當加工溫度降低之後,可避免其他層體(例如前述的內側聚烯烴層)的物理特性,在黏合的過程中被改變。於一示範實施例中,改質聚烯烴高分子的熔點為60°C至90°C。較佳的,改質聚烯烴高分子的熔點為75°C至85°C。
另外,改質聚烯烴高分子的熔融指數為6克/10分鐘至30克/10分鐘。較佳的,改質聚烯烴高分子的熔融指數9克/10分鐘至20克/10分鐘。改質聚烯烴高分子的熔融指數,是在120°C的溫度,負荷2.16公斤條件下進行測量。
改質聚烯烴高分子的改性基結構中含有馬來酸酐,於一示範實施例中,改質聚烯烴高分子的酸價為0.1 mgKOH/g至10 mgKOH/g。較佳的,改質聚烯烴高分子的酸價為4 mgKOH/g至8 mgKOH/g。
另外,本發明控制改質聚烯烴高分子的分子量,可兼具提升聚烯烴膠的加工性,以及提升鋁箔層10與內側聚烯烴層20之間結合性的效果。
詳細來說,改質聚烯烴高分子的分子量為100000克/莫耳至200000克/莫耳。較佳的,改質聚烯烴高分子的分子量為130000克/莫耳至170000克/莫耳。當改質聚烯烴高分子的分子量高於200000克/莫耳,聚烯烴膠的黏度會過高,產生不易塗佈加工的問題。當改質聚烯烴高分子的分子量低於100000克/莫耳,則會負面影響聚烯烴膠的黏合效果。
請參閱圖2所示,本發明鋰電池用鋁塑膜的製造方法包括:塗佈聚酯膠於鋁箔層上(步驟S1);設置外側層於聚酯膠上(步驟S2);烘乾聚酯膠,以於鋁箔層與外側層之間形成聚酯膠層(步驟S3)。熔融混煉加工聚烯烴膠粒與一改質劑,以形成一改質膠粒(步驟S4);添加一混合溶劑溶解改質膠粒,並加入硬化劑,以形成聚烯烴膠(步驟S5);塗佈聚烯烴膠於鋁箔層的另外一面上(步驟S6);設置內側聚烯烴層於聚烯烴膠上(步驟S7);烘乾聚烯烴膠,以於鋁箔層與內側聚烯烴層之間形成聚烯烴膠層(步驟S8)。
值得說明的是,本發明的聚烯烴膠的配製方式,包括上述步驟S4及步驟S5。
在步驟S4中,於160°C至230°C的溫度下,熔融混煉聚烯烴膠粒與改質劑。在混煉的過程中,聚烯烴膠粒會與改質劑發生反應,改質劑接枝於丙烯無規共聚物上,並形成前述的改質聚烯烴高分子。將改質聚烯烴高分子投入押出機後,可押出製得改質膠粒。
於一示範實施例中,聚烯烴膠粒的材料是丙烯無規共聚物。改質劑是選自於由下列所構成的群組:馬來酸酐、甲基四氫苯酐、轉位四氫苯酐、四氫苯酐、甲基六氫苯酐、甲基納迪克酸酐及2,3-萘二甲酸酐。相對於100重量份的聚烯烴膠粒,改質劑的添加量為0.5重量份至1.5重量份。補充說明,改性基的具體接枝量是以酸價進行定量,改質劑的添加量僅為方便說明操作步驟。
在步驟S5中,調配特定組分的混合溶劑溶解改質膠粒,再於其中加入硬化劑,即可配製完成本發明的聚烯烴膠。聚烯烴膠的黏度為50 cps至200 cps,固型份為12%至18%,但本發明不限於此。
本發明選用一非極性溶劑與一極性溶劑作為混合溶劑,通過特定成分與比例的混合溶劑,可調配出加工性佳,且具有良好接著性的聚烯烴膠。於一示範實施例中,非極性溶劑的添加量大於極性溶劑的添加量。當極性溶劑的添加量大於非極性溶劑時,聚烯烴膠會析出塊狀聚烯烴,而無法進行加工。較佳的,非極性溶劑與極性溶劑的比例為4:1至3:2。
舉例來說,非極性溶劑可以是甲基環己烷、環己烷、正己烷或其組合物。極性溶劑可以是甲乙酮、乙酸乙酯、甲基異丁基酮、醋酸正丙酯或其組合物。較佳的,非極性溶劑為甲基環己烷,極性溶劑為甲乙酮、乙酸乙酯或其混合物。舉例來說,硬化劑可以是Desmodur
®ultra N3300、Desmodur
®ultra N3600或其組合物。
為了證實本發明的鋰電池用鋁塑膜具有良好的耐電解液密著強度,即使長時間處於高溫環境,仍可保有良好的耐電解液密著強度,根據上述步驟S1至S8製得實施例1至3以及比較例1、2的鋁塑膜。
[實施例1至3]
使用型號為8021、厚度為40微米的鋁箔作為鋁箔層。選用材料為丙烯無規共聚物(由乙烯單體、丙烯單體及丁烯單體聚合而成)的聚烯烴膠粒,使聚烯烴膠粒與改質劑於220°C的溫度下熔融混煉,並經由押出機製成改質膠粒。使用非極性溶劑以及極性溶劑溶解改質膠粒,並添加適量的硬化劑,配製形成聚烯烴膠。在實施例1至3中,選用甲基環己烷(methylcyclohexane,MCH)作為非極性溶劑,選用甲乙酮(methyl ethyl ketone,MEK)與乙酸乙酯(ethyl acetate,EAC)作為極性溶劑。
接著,於鋁箔層的其中一面上塗佈聚烯烴膠,並將型號為DG、厚度為40微米的無延伸聚丙烯薄膜置於聚烯烴膠上,作為內側聚烯烴層,並形成一疊層結構。將上述疊層結構於105°C的溫度下烘乾,聚烯烴膠形成厚度為4微米的聚烯烴膠層。
於鋁箔層的另外一面上塗佈聚酯膠,並將型號為RX-F、厚度為25微米的聚酯層置於聚酯膠上,作為外側層。接著,於105°C的溫度下烘乾,聚酯膠形成厚度為4微米的聚酯層。
實施例1至3中使用的材料以及操作方式類似,其差異在於:聚烯烴膠粒的分子量不同,但都落於100000克/莫耳至200000克/莫耳的範圍內。
[比較例1、2]
比較例1、2的操作方式與實施例1至3的操作方式類似,其差異在於:聚烯烴膠粒的分子量並非落於100000克/莫耳至200000克/莫耳的範圍內,故於此不再贅述。
[比較例3]
比較例3的操作方式與實施例1至3的操作方式類似,其差異在於:丙烯無規共聚物並未經改質劑改質(酸價為0),而是直接以非極性溶劑與極性溶劑配製形成聚烯烴膠,具體步驟說明如下。
使用型號為8021、厚度為40微米的鋁箔作為鋁箔層。選用材料為丙烯無規共聚物(由乙烯單體、丙烯單體及丁烯單體聚合而成)的聚烯烴膠粒。使用非極性溶劑以及極性溶劑溶解改質膠粒,並添加適量的硬化劑,配製形成聚烯烴膠。在比較例1至3中,選用甲基環己烷(methylcyclohexane,MCH)作為非極性溶劑,選用甲乙酮(methyl ethyl ketone,MEK)與乙酸乙酯(ethyl acetate,EAC)作為極性溶劑。
接著,於鋁箔層的其中一面上塗佈聚烯烴膠,並將型號為DG、厚度為40微米的無延伸聚丙烯薄膜置於聚烯烴膠上,作為內側聚烯烴層,並形成一疊層結構。將上述疊層結構於105°C的溫度下烘乾,聚烯烴膠形成厚度為4微米的聚烯烴膠層。
於鋁箔層的另外一面上塗佈聚酯膠,並將型號為RX-F、厚度為25微米的聚酯層置於聚酯膠上,作為外側層。接著,於105°C的溫度下烘乾,聚酯膠形成厚度為4微米的聚酯層。
[比較例4]
比較例4的操作方式與比較例3的操作方式類似,皆是使用未改質的聚烯烴膠,其差異在於:比較例4是使用市面上可得的聚烯烴膠(型號為ZAR-1902B),直接塗佈於鋁箔層上以形成聚烯烴膠層,具體步驟說明如下。
使用型號為8021、厚度為40微米的鋁箔作為鋁箔層。於鋁箔層的其中一面上塗佈聚烯烴膠,並將型號為DG、厚度為40微米的無延伸聚丙烯薄膜置於聚烯烴膠上,作為內側聚烯烴層,並形成一疊層結構。將上述疊層結構於105°C的溫度下烘乾,聚烯烴膠形成厚度為4微米的聚烯烴膠層。
於鋁箔層的另外一面上塗佈聚酯膠,並將型號為RX-F、厚度為25微米的聚酯層置於聚酯膠上,作為外側層。接著,於105°C的溫度下烘乾,聚酯膠形成厚度為4微米的聚酯層。
表1列出實施例1至3與比較例1至3在步驟S4中,聚烯烴膠粒與改質劑的成分、特性與添加量,若無特別標註單位,則單位為重量份。表2列出實施例1至3與比較例1至3在步驟S5中,改質膠粒或聚烯烴膠粒、非極性溶劑、極性溶劑與硬化劑的成分、特性與添加量,若無特別標註單位,則單位為重量份。
表3列出實施例1至3與比較例1至4中的鋁塑膜,進行密著強度測試的結果。在密著強度測試中,先將前述鋁塑膜裁切成長寬尺寸為150毫米×15毫米的樣品,再以刀片輕劃樣品,於距樣品短邊15毫米的位置,形成平行於樣品短邊方向的割線。沿割線反覆摺疊數次後,緩慢自鋁箔層上剝離無延伸聚丙烯薄膜,待無延伸聚丙烯薄膜與鋁箔層完整分離10毫米以上之後,測量無延伸聚丙烯薄膜與鋁箔層的密著強度,便可獲得初始的密著強度。
再取另一樣品浸泡於溫度為85°C,型號為FPC-301的電解液中168小時,再重複上述形成割線、剝離無延伸聚丙烯薄膜以及測量密著強度的步驟,可獲得浸泡電解液後的鋁塑膜密著強度。
在剝離測試中,夾頭相距50毫米,剝離方式為T型測試法,剝離測試速度為200毫米/分鐘,工作距離為50毫米以上。型號為FPC-301的電解液中包括濃度為1M的六氟磷酸鋰(LiPF
6),溶劑為重量比例為1:1:1的碳酸乙烯酯(EC)、碳酸二乙酯(DEC)及碳酸二甲酯(DMC)。
表1
(重量份) | 實施例1 | 實施例2 | 實施例3 | 比較例1 | 比較例2 | 比較例3 | |
聚烯烴膠粒 | 種類 | 丙烯無規共聚物 | 丙烯無規共聚物 | 丙烯無規共聚物 | 丙烯無規共聚物 | 丙烯無規共聚物 | 丙烯無規共聚物 |
組成 | 由乙烯單體、丙烯單體及丁烯單體聚合而成 | ||||||
分子量(g/mol) | 10萬 | 15萬 | 20萬 | 7萬 | 22萬 | 15萬 | |
添加量 | 100 | 100 | 100 | 100 | 100 | 100 | |
改質劑 | 種類 | 馬來酸酐 | 馬來酸酐 | 馬來酸酐 | 馬來酸酐 | 馬來酸酐 | 未改質 |
添加量 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 0 |
表2
(重量份) | 實施例1 | 實施例2 | 實施例3 | 比較例1 | 比較例2 | 比較例3 | ||
改質 膠粒/聚烯烴膠粒 | 添加量 | 20 | 20 | 20 | 20 | 20 | 20 | |
酸價(mgKOH/g) | 5.8 | 5.8 | 5.8 | 5.8 | 5.8 | 0 | ||
非極性溶劑 | 種類 | MCH | MCH | MCH | MCH | MCH | MCH | |
添加量 | 56 | 56 | 56 | 56 | 56 | 56 | ||
極性 溶劑 | 種類 | MEK與EAC | MEK與EAC | MEK與EAC | MEK與EAC | MEK與EAC | MEK與EAC | |
添加量 | 24 | 24 | 24 | 24 | 24 | 24 | ||
非極性溶劑與 極性溶劑的比例 | 70/30 | 70/30 | 70/30 | 70/30 | 70/30 | 70/30 | ||
硬化劑 | 種類 | NCO | NCO | NCO | NCO | NCO | NCO | |
添加量 | 3.5 | 3.5 | 3.5 | 3.5 | 3.5 | 3.5 | ||
表3
(N/15mm) | 實施例1 | 實施例2 | 實施例3 | 比較例1 | 比較例2 | 比較例3 | 比較例4 | |
密著 強度 | 初始 | 15.3 | 15.5 | 15.6 | 14.9 | 14.3 | 15.4 | 14.0 |
浸泡電解液後 | 12.8 | 13.7 | 13.1 | 8.2 | 11.6 | 2.1 | 10.5 |
根據表3的結果,本發明的鋁塑膜具有良好的耐電解液密著強度(大於15 N/15mm),即便長時間處於高溫且與電解液接觸的環境下,仍可具有良好的耐電解液密著強度(大於12 N/15mm)。較佳的,本發明的鋁塑膜的耐電解液密著強度為15.2 N/15mm至18 N/15mm。於85°C的溫度下168小時後,鋁塑膜的耐電解液密著強度為12 N/15mm至16 N/15mm。
由比較例3可得知,相較於使用未改質的聚烯烴高分子,使用本發明的改質聚烯烴高分子,可大幅提升鋁塑膜的耐電解液密著強度,尤其是提升鋁塑膜長時間處於高溫且與電解液接觸後的耐電解液密著強度。
由比較例4可得知,相較於市面上的聚烯烴膠,使用本發明的改質聚烯烴高分子,可使鋁塑膜具有較佳的耐電解液密著強度,其是市面上聚烯烴膠所無法達到的效果。
由比較例1、2得知,控制改質聚烯烴高分子的分子量為100000克/莫耳至200000克/莫耳,可使鋁塑膜具有良好的耐電解液密著強度。一旦改質聚烯烴高分子的分子量低於100000克/莫耳,或是高於200000克/莫耳,則無法達到本發明具良好耐電解液密著強度的功效。
[實施例的有益效果]
本發明的其中一有益效果在於,本發明所提供的鋰電池用鋁塑膜及其製造方法,其能通過“改質聚烯烴高分子具有改性基,改性基的結構中含有馬來酸酐”以及“改質聚烯烴高分子的分子量為100000克/莫耳至200000克/莫耳”的技術方案,以提升鋰電池用鋁塑膜的耐電解液密著強度。
更進一步來說,本發明選用特殊的聚烯烴膠,尤其是聚烯烴膠中的改質聚烯烴高分子。本發明選用丙烯無規共聚物作為改質聚烯烴高分子的主要材料,並使用結構中含馬來酸酐的改質劑來修飾丙烯無規共聚物,使得丙烯無規共聚物上接枝有結構中含有馬來酸酐的改性基。除了成分的選用之外,本發明還控制改質聚烯烴高分子的特性(酸價、分子量、熔點、熔融指數)。如此一來,可調整丙烯無規共聚物的特性,在不負面影響聚烯烴膠黏合效果的前提下,提升鋁塑膜的耐電解液密著強度,並且,聚烯烴膠還具有容易加工的優勢。
以上所公開的內容僅為本發明的優選可行實施例,並非因此侷限本發明的申請專利範圍,所以凡是運用本發明說明書及圖式內容所做的等效技術變化,均包含於本發明的申請專利範圍內。
10:鋁箔層
11:防蝕處理層
12:防蝕處理層
20:內側聚烯烴層
30:外側層
40:聚烯烴膠層
50:聚酯膠層
圖1為本發明鋰電池用鋁塑膜的結構側視圖。
圖2為本發明鋰電池用鋁塑膜的製造方法的流程示意圖。
10:鋁箔層
11:防蝕處理層
12:防蝕處理層
20:內側聚烯烴層
30:外側層
40:聚烯烴膠層
50:聚酯膠層
Claims (9)
- 一種鋰電池用鋁塑膜的製造方法,其包括:配製一聚烯烴膠;所述聚烯烴膠的成分包括一改質聚烯烴高分子與一硬化劑;其中,所述改質聚烯烴高分子具有一改性基,所述改性基的結構中含有馬來酸酐,所述改質聚烯烴高分子的分子量為100000克/莫耳至200000克/莫耳;塗佈所述聚烯烴膠於一鋁箔層的其中一面上;設置一內側聚烯烴層於所述聚烯烴膠上;以及烘乾所述聚烯烴膠,以於所述鋁箔層與所述內側聚烯烴層之間形成一聚烯烴膠層;其中,配製所述聚烯烴膠的步驟包括:添加一混合溶劑溶解一改質膠粒,再加入所述硬化劑,以形成所述聚烯烴膠;所述改質膠粒的材料是所述改質聚烯烴高分子,所述混合溶劑包含一非極性溶劑與一極性溶劑,所述非極性溶劑與所述極性溶劑的質量比例為4:1至3:2;其中,所述非極性溶劑為甲基環己烷,所述極性溶劑為甲乙酮與乙酸乙酯的混合物。
- 如請求項1所述的製造方法,其中,所述改質聚烯烴高分子的酸價為0.1mgKOH/g至10mgKOH/g。
- 如請求項1所述的製造方法,其中,配製所述聚烯烴膠的步驟包括:於160℃至230℃的溫度下,熔融混合一聚烯烴膠粒與一改質劑,以形成一改質膠粒,使用所述改質膠粒配製成所述聚烯烴膠;其中,所述改質膠粒的材料是所述改質聚烯烴高分子。
- 如請求項3所述的製造方法,其中,所述改質劑的結構中含有馬來酸酐。
- 如請求項1所述的製造方法,其中,所述改質聚烯烴高分子是 一馬來酸酐改質的丙烯無規共聚物,以所述馬來酸酐改質的丙烯無規共聚物的總重為基礎,丙烯單體在所述馬來酸酐改質的丙烯無規共聚物中的含量大於50重量百分比。
- 如請求項1所述的製造方法,其中,所述改質聚烯烴高分子是一馬來酸酐改質的丙烯無規共聚物,所述馬來酸酐改質的丙烯無規共聚物的共聚單體包含乙烯單體、丙烯單體與丁烯單體。
- 如請求項1所述的製造方法,其中,所述改質聚烯烴高分子的熔點為60℃至90℃,所述改質聚烯烴高分子在120℃、負荷2.16公斤條件下測量的熔融指數為6克/10分鐘至30克/10分鐘。
- 如請求項1所述的製造方法,進一步包括:塗佈一聚酯膠於所述鋁箔層的另外一面上;設置一外側層於所述聚酯膠上,所述外側層是尼龍層或聚酯層;以及烘乾所述聚酯膠,以於所述鋁箔層與所述外側層之間形成一聚酯膠層。
- 一種鋰電池用鋁塑膜,其是由如請求項1至8中任一項所述的鋰電池用鋁塑膜的製造方法製成,所述聚烯烴膠層與所述鋁箔層的耐電解液密著強度大於15N/15mm;置於85℃的溫度下168小時後,所述聚烯烴膠層與所述鋁箔層的耐電解液密著強度大於12.5N/15mm。
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CN202211434035.7A CN117984626A (zh) | 2022-11-04 | 2022-11-16 | 锂电池用铝塑膜及其制造方法 |
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CN114678637A (zh) * | 2022-04-18 | 2022-06-28 | 江苏睿捷新材料科技有限公司 | 一种锂离子电池包装用铝塑复合膜及电池 |
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CN114678637A (zh) * | 2022-04-18 | 2022-06-28 | 江苏睿捷新材料科技有限公司 | 一种锂离子电池包装用铝塑复合膜及电池 |
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