TWI584517B - 用於製備撓性多孔膜的方法 - Google Patents

用於製備撓性多孔膜的方法 Download PDF

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TWI584517B
TWI584517B TW104117614A TW104117614A TWI584517B TW I584517 B TWI584517 B TW I584517B TW 104117614 A TW104117614 A TW 104117614A TW 104117614 A TW104117614 A TW 104117614A TW I584517 B TWI584517 B TW I584517B
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flexible
electrospinning
substrate
copolymer
pvdf
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劉晨敏
蔡力鋒
黃嘉勤
蔡丞恩
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納米及先進材料研發院有限公司
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Description

用於製備撓性多孔膜的方法 相關申請的交叉參考
本申請要求2014年6月16日提交的U.S臨時申請No.61/998,017和2015年5月26日提交的美國非臨時申請No.14/721,002的優先權，兩個申請的內容藉由援引整體併入本文。
本發明涉及一種使用靜電紡絲技術製備的撓性多孔膜。撓性多孔膜的一個應用是用於製備撓性鋰離子電池。
如本文中使用的，“撓性”物體(諸如撓性電池、撓性薄膜或撓性膜)是具有可調整形狀的固態非剛性物體。如此，該撓性物體是可彎曲且可壓擠的。
薄膜撓性鋰離子(Li-離子)電池有利地用於需要小電源的各種應用。根據使用者的需要，可以以不同的形狀和尺寸製造撓性電池。藉由調整電池的形狀來適配裝置中的可用空間，電池在佔用裝置中無用空間和只增加微不足道的重量的同時，還能提供需用功率。在製備撓性電池期間，最有挑戰性的部分是準備用在電池中的電解質。由於電解質通常是液體形式，所以需要使用用電解質浸透的多孔膜，以在膜中保留電解質。該膜通常被稱為電池的分離器。當彎曲或重塑電池時，電解質有從膜中洩 漏引起電池的電壓變化的風險，因此會影響電池的可靠性。希望具有即使當彎曲或重塑該膜時也能高度可靠地將電介質保留在其中的多孔膜。
在2010年，ACS Nano，第4卷第10期，5843-5848頁，L.Hu、H.Wu、F.La Mantia、Y.Yang和Y.Cui的“Thin,flexible secondary Li-ion paper batteries”的公開中(藉由援引將其整體併入本文)，使用紙作為撓性鋰離子電池的分離器。雖然獲得了撓韌性，但不能調整紙的多孔性，以致電池的充電率/傳導率不可調。此外，在通常存在於電解質中的溶劑存在的情況下，紙是不穩定的。在長時間沉浸在溶劑中之後，紙分離器會變軟並破碎，使得其中的液體電解質漏出並引起短路。
在2012年6月28日，Scientific reports，第2卷第481期，N.Singh等人的“Paintable battery”的公開中(藉由援引將其整體併入本文)，使用聚合物塗料作為電池的分離器。雖然當電池彎曲時，似乎不具有洩漏問題，但是聚合物塗料的孔隙率和傳導性會降低，導致低的充電率，以致與常規鋰離子電池相比，所需的充電時間增多。
本領域需要有撓性的、具有高孔隙率的且即使當重塑該膜時在不洩露的情況下也能保留其中液體的多孔膜。這種膜的一個有利應用是製備撓性鋰離子電池。通常，如果重塑這種膜，這種膜可用於需要在不洩露的情況下保持其中液體的其它應用。
本發明提供一種用於製備撓性多孔膜的方法。該方法包括用靜電紡絲製程在撓性基板的第一表面上沉積第一靜電紡絲層。具體地，靜電紡絲製程包括在多個製程參數下，將纖維從基本同質的溶液靜電紡絲到 基板上。該溶液包括分散在溶劑中的聚二氟亞乙烯(polyvinylidene fluoride；PVDF)和聚(二氟亞乙烯-六氟丙烯)(poly(vinylidene fluoride-hexafluoropropylene)；PVdF-HFP)共聚物，使得該溶液具有在300cP至1500cP之間的聚合物黏度。多個製程參數包括：在20kV至50kV之間的電壓、在3ml/h至12ml/h之間的饋送率以及在100mm至150mm之間的旋轉高度。
較佳地，共聚物中使用的PVDF和PVdF-HFP具有在1：1和5：1之間的重量比。
還較佳地，該溶劑包括二甲基甲醯胺(DMF)和丙酮。另外，溶液中使用的DMF和丙酮可具有在1：2和8：2之間的重量比。
一個較佳設置是共聚物的重量是共聚物和溶劑總重量的5%至25%。
多個製程參數可進一步包括在20%至50%之間的環境濕度。
較佳地，基板由聚丙烯(PP)或聚乙烯(PE)組成，或者為三層PP/PE/PP電解分離膜。
撓性電池藉由包括固體電解質來實現，該固體電解質包括用公開的方法形成的撓性多孔膜。該膜進一步用液體電解質浸透。
本發明的其它方面如由下文中的實施例所示例那樣公開。
如說明書和附屬權利要求中使用的，在第一值和第二值“之間”的參數意指，該參數具有在第一值至第二值範圍中的包含第一值和第二值的值。這意味著該參數可以具有等於第一值或第二值的值。
在本發明的開發期間，發明人首先著重研究了製造撓性鋰離子電池的具體應用，並使用特定的靜電紡絲技術在商用分離器的每一側上製備成直線的納米纖維膜以製造夾層結構或獨立的納米纖維墊。發明人發現，納米纖維層具有非常好的電解質吸收率，其能接受本身重量10倍的液體電解質，同時在電池操作期間，商用分離器能充當非常好的機械支撐以避免任何損壞和變形。該膜還具有高孔隙率。膜的高孔隙率和電極結構的適當選擇使用聚合物凝膠能緩解固體電解質的緩慢的品質運輸問題。此外，多孔網狀物的高吸收能力消除了對電解質的剛性容器的需要。開發的固體電解質和電極材料的適當選擇一起有利地用於提高撓性鋰離子電池的安全性、撓韌性、離子傳導率和能量密度。
本發明的一方面是製備撓性多孔膜的方法。在闡述的本文公開的撓性多孔膜的細節中，我們著重研究用所公開的膜製備撓性鋰離子電池的應用。然而，本文公開的多孔膜不只限制於該應用。該公開膜還適用於其它應用。
在詳述該公開的方法之前，在圖1中描繪了用該方法形成的膜100的結構。膜100包括基板110，該基板110具有沉積在之上以形成夾 層結構的兩個多孔層120、130。當該膜100用於在撓性鋰離子電池中形成固體電解質時，在用液體電解質浸透之後，需要該夾層結構。然而，其它潛在的應用可以需要或較佳兩個表面中的僅一個表面沉積有多孔層。當不同地處理或完成另一個表面時，一些其它的潛在應用還需要只有一個表面具有多孔層。通常，膜100包括基板和在基板110上的至少一個多孔層(120或130)。每個多孔層都藉由靜電紡絲來形成。在不失一般性的情況下，多孔層120和130分別被稱為第一靜電紡絲層120和第二靜電紡絲層130。
示例地，該方法包括用靜電紡絲製程在基板110的第一表面111上沉積第一靜電紡絲層120。具體地，基板110是撓性的。可選地，該方法進一步包括用靜電紡絲製程在基板110的第二表面112上沉積第二靜電紡絲層130。注意，第二表面112和第一表面111相對。
為了使膜100具有高的孔隙率和撓性的特性以及即使彎曲或重塑膜100也能將液體保留在其中的能力，在靜電紡絲製程中使用的參數是很重要的。雖然本發明不意圖被任何理論限制，但是發明人認為，如果與用常用的靜電紡絲技術來實現相比，形成靜電紡絲層(120或130)的納米纖維封裝更緊密，則存在液體分子更牢固地保留在由納米纖維形成的網狀物內的機會。該較高的液體保留能力有利地用於抵制由彎曲或重塑靜電紡絲層引入的外力，防止了靜電紡絲層中的液體洩漏。鑒於該原因，發明人進行了實驗，並確定了較佳的一組溶液成分和在靜電紡絲製程中使用的製程參數。
圖2描述了實現靜電紡絲製程的典型機構。靜電紡絲製程包括在多個製程參數下，將纖維220從基本同質的溶液210靜電紡絲到基板 230上。溶液210包含在注射器215中，並經由噴絲頭217以饋送率251噴出，噴絲頭217旋轉，以使纖維220螺旋地落在基板230上以在其上形成靜電紡絲層。高壓電源218用於在噴絲頭217和基板230之間提供電壓252。示例性的較佳的一組溶液成分和製程參數給出如下。溶液210包括分散在溶劑中的聚二氟亞乙烯(PVDF)和聚(二氟亞乙烯-六氟丙烯)(PVdF-HFP)共聚物，以使該溶液具有在300cP至1500cP之間的聚合物黏度。多個製程參數包括電壓252、饋送率251和旋轉高度253，其中電壓252在20kV至50kV之間，饋送率251在3ml/h至12ml/h之間，旋轉高度253在100mm至150mm之間。
在一個較佳設置中，共聚物中使用的PVDF和PVdF-HFP具有在1：1和5：1之間的重量比。
實際上且較佳地，用於分散共聚物的溶劑包括二甲基甲醯胺(DMF)和丙酮。較佳設置是溶液中使用的DMF和丙酮具有在1：2和8：2之間的重量比。
在另一個較佳設置中，共聚物具有占共聚物和溶劑的總重量的5%至25%的重量。
多個製程參數可進一步包括環境濕度。該環境濕度具有20%至50%的較佳範圍。
在靜電紡絲製程期間，還需要控制噴絲頭217的噴絲速度和旋轉速度。噴絲速度和旋轉速度的典型值分別為20毫米/秒和每分鐘2000轉。
實際上，希望從商業上可獲得的列表選擇基板230。具體地， 尤其是對於製造撓性鋰離子電池的應用，基板較佳由聚丙烯(PP)或聚乙烯(PE)組成，或者為三層PP/PE/PP電解分離膜。
圖3描述了可由用該公開方法製造的膜實現的撓性電池的實例。撓性電池300包括固體電解質310。該固體電解質310包括用上述公開的方法的任何一個實施例形成的撓性多孔膜。此外，該膜用液體電解質浸透。對於是鋰離子電池的撓性電池300，液體電解質可以從LiPF6、LiClO4、(C2H5)4AN、H2O、H2SO4、NaOH、NaCl或其組合中選擇。
基於如上述公開的固體電解質310，本領域的普通技術人員能夠使用現有的電池設計來實現撓性電池。例如，藉由上述的L.Hu、H.Wu、F.La Mantia、Y.Yang和Y.Cui的公開得到一種撓性電池結構。在撓性電池300中，固體電解質310夾在陽極320和陰極330之間。佈置第一集電器341和第二集電器342以分別接觸陽極320和陰極330接觸。分別用第一鋁塑板351和第二鋁塑板352進一步封裝第一集電器341和第二集電器342。
在不偏離本發明的精神或基本特徵的情況下，可以以其它具體形式具體化本發明。因此，本實施例在所有方面都被認為是示例性的而不是限制性的。本發明的範圍用附加的權利要求，而不是前面的描述來表明，因此，在權利要求的等效意義和範圍內進行的所有改變都意指被包含在內。
100‧‧‧膜
110‧‧‧基板
111‧‧‧第一表面
112‧‧‧第二表面
120‧‧‧多孔層
130‧‧‧多孔層
210‧‧‧溶液
215‧‧‧注射器
217‧‧‧噴絲頭
218‧‧‧高壓電源
220‧‧‧纖維
230‧‧‧基板
251‧‧‧饋送率
252‧‧‧電壓
253‧‧‧旋轉高度
300‧‧‧撓性電池
310‧‧‧固體電解質
320‧‧‧陽極
330‧‧‧陰極
341‧‧‧集電器
342‧‧‧集電器
351‧‧‧鋁塑板
352‧‧‧鋁塑板
圖1描述了根據本發明的一個實施例實現的撓性多孔膜的結構，其中該膜包括被每個均由靜電紡絲製程形成的兩個多孔層夾住的基板。
圖2描述了實現本發明所公開的靜電紡絲製程的典型機構。
圖3描述了可用公開的膜實現的撓性電池的實例。
300‧‧‧撓性電池
310‧‧‧固體電解質
320‧‧‧陽極
330‧‧‧陰極
341‧‧‧集電器
342‧‧‧集電器
351‧‧‧鋁塑板
352‧‧‧鋁塑板

Claims (8)

  1. 一種用於製備撓性多孔膜的方法，其包括：藉由靜電紡絲製程在撓性基板的第一表面上沉積第一靜電紡絲層；其中：該靜電紡絲製程包括在多個製程參數下，將纖維從基本同質的溶液靜電紡絲到基板上；該溶液包括分散在溶劑中的聚二氟亞乙烯(polyvinylidene fluoride；PVDF)和聚(二氟亞乙烯-六氟丙烯)(poly(vinylidene fluoride-hexafluoropropylene)；PVdF-HFP)共聚物，以使該溶液具有在300cP至1500cP之間的聚合物黏度；和該多個製程參數包括：在20kV至50kV之間的電壓；在3ml/h至12ml/h之間的饋送率；及在100mm至150mm之間的旋轉高度。
  2. 根據申請專利範圍第1項之方法，其中該共聚物中使用的PVDF和PVdF-HFP具有在1：1和5：1之間的重量比。
  3. 根據申請專利範圍第1項之方法，其中該溶劑包括二甲基甲醯胺(DMF)和丙酮。
  4. 根據申請專利範圍第3項之方法，其中該溶液中使用的DMF和丙酮具有在1：2和8：2之間的重量比。
  5. 根據申請專利範圍第1項之方法，其中該共聚物的重量是共聚物和溶劑的總重量的5%至25%。
  6. 根據申請專利範圍第1項之方法，其中該多個製程參數進一步包括：在20%至50%之間的環境濕度。
  7. 根據申請專利範圍第1項之方法，其中基板由聚丙烯(PP)或聚乙烯(PE)組成，或者為三層PP/PE/PP電解分離膜。
  8. 根據申請專利範圍第1項之方法，其進一步包括：藉由靜電紡絲製程在基板的第二表面上沉積第二靜電紡絲層，該第二表面與該第一表面相對。
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