CN105186005A - 柔性多孔膜 - Google Patents

柔性多孔膜 Download PDF

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CN105186005A
CN105186005A CN201510335200.7A CN201510335200A CN105186005A CN 105186005 A CN105186005 A CN 105186005A CN 201510335200 A CN201510335200 A CN 201510335200A CN 105186005 A CN105186005 A CN 105186005A
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flexible
electrostatic spinning
pvdf
copolymer
solvent
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刘晨敏
蔡力锋
黄嘉勤
蔡丞恩
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Nano and Advanced Materials Institute Ltd
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Abstract

本发明提供了一种用于制备柔性多孔膜的方法。膜的一个应用是用于制备柔性锂离子电池。该方法包括：通过静电纺丝在柔性衬底上沉积至少一个静电纺丝层。静电纺丝中使用的溶液包括分散在溶剂中的聚偏二氟乙烯(PVDF)和聚(偏氟乙烯-六氟丙烯)(PVdF-HFP)共聚物，以使该溶液具有在300cP至1500cP之间的聚合物粘度。静电纺丝工艺参数的优选设置包括在20kV和50kV之间的电压、在3ml/h和12ml/h之间的馈送率和在100mm和150mm之间的旋转高度。优选地，PVDF和PVdF-HFP具有在1:1和5:1之间的重量比。溶剂可包括重量比在1:2和8:2之间的二甲基甲酰胺(DMF)和丙酮。共聚物的重量优选为共聚物和溶剂总重量的5％至25％。

Description

柔性多孔膜
相关申请的交叉参考
本申请要求2014年6月16日提交的U.S临时申请No.61/998,017和2015年5月26日提交的美国非临时申请No.14/721,002的优先权，两个申请的公开内容通过援引整体并入本文。
技术领域
本发明涉及一种使用静电纺丝技术制备的柔性多孔膜。柔性多孔膜的一个应用是用于制备柔性锂离子电池。
背景技术
如本文中使用的，“柔性”物体(诸如柔性电池、柔性薄膜或柔性膜)是具有可调整形状的固态非刚性物体。如此，该柔性物体是可弯曲且可压挤的。
薄膜柔性锂离子(Li-离子)电池有利地用于需要小电源的各种应用。根据用户的需要，可以以不同的形状和尺寸制造柔性电池。通过调整电池的形状来适配装置中的可用空间，电池在占用装置中无用空间和只增加微不足道的重量的同时，还能提供需用功率。在制备柔性电池期间，最有挑战性的部分是准备用在电池中的电解质。由于电解质通常是液体形式，所以需要使用用电解质浸透的多孔膜，以在膜中保留电解质。该膜通常被称为电池的分离器。当弯曲或重塑电池时，电解质有从膜中泄漏引起电池的电压变化的风险，因此会影响电池的可靠性。希望具有即使当弯曲或重塑该膜时也能高度可靠地将电介质保留在其中的多孔膜。
在2010年，ACSNano，第4卷第10期，5843-5848页，L.Hu、H.Wu、F.LaMantia、Y.Yang和Y.Cui的“Thin,flexiblesecondaryLi-ionpaperbatteries”的公开中(通过援引将其整体并入本文)，使用纸作为柔性锂离子电池的分离器。虽然获得了柔韧性，但不能调整纸的多孔性，以致电池的充电率/传导率不可调。此外，在通常存在于电解质中的溶剂存在的情况下，纸是不稳定的。在长时间沉浸在溶剂中之后，纸分离器会***并破碎，使得其中的液体电解质漏出并引起短路。
在2012年6月28日，Scientificreports，第2卷第481期，N.Singh等人的“Paintablebattery”的公开中(通过援引将其整体并入本文)，使用聚合物涂料作为电池的分离器。虽然当电池弯曲时，似乎不具有泄漏问题，但是聚合物涂料的孔隙率和传导性会降低，导致低的充电率，以致与常规锂离子电池相比，所需的充电时间增多。
本领域需要有柔性的、具有高孔隙率的且即使当重塑该膜时在***露的情况下也能保留其中液体的多孔膜。这种膜的一个有利应用是制备柔性锂离子电池。通常，如果重塑这种膜，这种膜可用于需要在***露的情况下保持其中液体的其它应用。
发明内容
本发明提供一种用于制备柔性多孔膜的方法。该方法包括用静电纺丝工艺在柔性衬底的第一表面上沉积第一静电纺丝层。具体地，静电纺丝工艺包括在多个工艺参数下，将纤维从基本同质的溶液静电纺丝到衬底上。该溶液包括分散在溶剂中的聚偏二氟乙烯(PVDF)和聚(偏氟乙烯-六氟丙烯)(PVdF-HFP)共聚物，使得该溶液具有在300cP至1500cP之间的聚合物粘度。多个工艺参数包括：在20kV和50kV之间的电压、在3ml/h和12ml/h之间的馈送率以及在100mm和150mm之间的旋转高度。
优选地，共聚物中使用的PVDF和PVdF-HFP具有在1:1和5:1之间的重量比。
还优选地，该溶剂包括二甲基甲酰胺(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之间的重量比。
一个优选设置是共聚物的重量是共聚物和溶剂总重量的5％至25％。
多个工艺参数可进一步包括在20％和50％之间的环境湿度。
优选地，衬底由聚丙烯(PP)或聚乙烯(PE)组成，或者为三层PP/PE/PP电解分离膜。
柔性电池通过包括固体电解质来实现，该固体电解质包括用公开的方法形成的柔性多孔膜。该膜进一步用液体电解质浸透。
本发明的其它方面如由下文中的实施例所示例那样公开。
附图说明
图1描述了根据本发明的一个实施例实现的柔性多孔膜的结构，其中该膜包括被每个均由静电纺丝工艺形成的两个多孔层夹住的衬底。
图2描述了实现本发明所公开的静电纺丝工艺的典型机构。
图3描述了可用公开的膜实现的柔性电池的实例。
具体实施方式
如说明书和附属权利要求中使用的，在第一值和第二值“之间”的参数意指，该参数具有在第一值至第二值范围中的包含第一值和第二值的值。这意味着该参数可以具有等于第一值或第二值的值。
在本发明的开发期间，发明人首先着重研究了制造柔性锂离子电池的具体应用，并使用特定的静电纺丝技术在商用分离器的每一侧上制备成直线的纳米纤维膜以制造夹层结构或独立的纳米纤维垫。发明人发现，纳米纤维层具有非常好的电解质吸收率，其能接受本身重量10倍的液体电解质，同时在电池操作期间，商用分离器能充当非常好的机械支撑以避免任何损坏和变形。该膜还具有高孔隙率。膜的高孔隙率和电极结构的适当选择使用聚合物凝胶能缓解固体电解质的缓慢的质量运输问题。此外，多孔网状物的高吸收能力消除了对电解质的刚性容器的需要。开发的固体电解质和电极材料的适当选择一起有利地用于提高柔性锂离子电池的安全性、柔韧性、离子传导率和能量密度。
本发明的一方面是制备柔性多孔膜的方法。在阐述的本文公开的柔性多孔膜的细节中，我们着重研究用所公开的膜制备柔性锂离子电池的应用。然而，本文公开的多孔膜不只限制于该应用。该公开膜还适用于其它应用。
在详述该公开的方法之前，在图1中描绘了用该方法形成的膜100的结构。膜100包括衬底110，该衬底110具有沉积在之上以形成夹层结构的两个多孔层120、130。当该膜100用于在柔性锂离子电池中形成固体电解质时，在用液体电解质浸透之后，需要该夹层结构。然而，其它潜在的应用可以需要或优选两个表面中的仅一个表面沉积有多孔层。当不同地处理或完成另一个表面时，一些其它的潜在应用还需要只有一个表面具有多孔层。通常，膜100包括衬底和在衬底110上的至少一个多孔层(120或130)。每个多孔层都通过静电纺丝来形成。在不失一般性的情况下，多孔层120和130分别被称为第一静电纺丝层120和第二静电纺丝层130。
示例地，该方法包括用静电纺丝工艺在衬底110的第一表面111上沉积第一静电纺丝层120。具体地，衬底110是柔性的。可选地，该方法进一步包括用静电纺丝工艺在衬底110的第二表面112上沉积第二静电纺丝层130。注意，第二表面112和第一表面111相对。
为了使膜100具有高的孔隙率和柔性的特性以及即使弯曲或重塑膜100也能将液体保留在其中的能力，在静电纺丝工艺中使用的参数是很重要的。虽然本发明不意图被任何理论限制，但是发明人认为，如果与用常用的静电纺丝技术来实现相比，形成静电纺丝层(120或130)的纳米纤维封装更紧密，则存在液体分子更牢固地保留在由纳米纤维形成的网状物内的机会。该较高的液体保留能力有利地用于抵制由弯曲或重塑静电纺丝层引入的外力，防止了静电纺丝层中的液体泄漏。鉴于该原因，发明人进行了实验，并确定了优选的一组溶液成分和在静电纺丝工艺中使用的工艺参数。
图2描述了实现静电纺丝工艺的典型机构。静电纺丝工艺包括在多个工艺参数下，将纤维220从基本同质的溶液210静电纺丝到衬底230上。溶液210包含在注射器215中，并经由喷丝头217以馈送率251喷出，喷丝头217旋转，以使纤维220螺旋地落在衬底230上以在其上形成静电纺丝层。高压电源218用于在喷丝头217和衬底230之间提供电压252。示例性的优选的一组溶液成分和工艺参数给出如下。溶液210包括分散在溶剂中的聚偏氟乙烯(PVDF)和聚(偏二氟乙烯-六氟丙烯)(PVdF-HFP)共聚物，以使该溶液具有在300cP至1500cP之间的聚合物粘度。多个工艺参数包括电压252、馈送率251和旋转高度253，其中电压252在20kV和50kV之间，馈送率251在3ml/h和12ml/h之间，旋转高度253在100mm和150mm之间。
在一个优选设置中，共聚物中使用的PVDF和PVdF-HFP具有在1：1和5：1之间的重量比。
实际上且优选地，用于分散共聚物的溶剂包括二甲基甲酰胺(DMF)和丙酮。优选设置是溶液中使用的DMF和丙酮具有在1:2和8:2之间的重量比。
在另一个优选设置中，共聚物具有占共聚物和溶剂的总重量的5％至25％的重量。
多个工艺参数可进一步包括环境湿度。该环境湿度具有20％至50％的优选范围。
在静电纺丝工艺期间，还需要控制喷丝头217的喷丝速度和旋转速度。喷丝速度和旋转速度的典型值分别为20毫米/秒和每分钟2000转。
实际上，希望从商业上可获得的列表选择衬底230。具体地，尤其是对于制造柔性锂离子电池的应用，衬底优选由聚丙烯(PP)或聚乙烯(PE)组成，或者为三层PP/PE/PP电解分离膜。
图3描述了可由用该公开方法制造的膜实现的柔性电池的实例。柔性电池300包括固体电解质310。该固体电解质310包括用上述公开的方法的任何一个实施例形成的柔性多孔膜。此外，该膜用液体电解质浸透。对于是锂离子电池的柔性电池300，液体电解质可以从LiPF6、LiClO4、(C2H5)4AN、H2O、H2SO4、NaOH、NaCl或其组合中选择。
基于如上述公开的固体电解质310，本领域的普通技术人员能够使用现有的电池设计来实现柔性电池。例如，通过上述的L.Hu、H.Wu、F.LaMantia、Y.Yang和Y.Cui的公开得到一种柔性电池结构。在柔性电池300中，固体电解质310夹在阳级320和阴极330之间。布置第一集电器341和第二集电器342以分别接触阳级320和阴极330接触。分别用第一铝塑板351和第二铝塑板352进一步封装第一集电器341和第二集电器342。
在不偏离本发明的精神或基本特征的情况下，可以以其它具体形式具体化本发明。因此，本实施例在所有方面都被认为是示例性的而不是限制性的。本发明的范围用附加的权利要求，而不是前面的描述来表明，因此，在权利要求的等效意义和范围内进行的所有改变都意指被包含在内。

Claims (13)

1.一种用于制备柔性多孔膜的方法，其包括：
通过静电纺丝工艺在柔性衬底的第一表面上沉积第一静电纺丝层；
其中：
该静电纺丝工艺包括在多个工艺参数下，将纤维从基本同质的溶液静电纺丝到衬底上；
该溶液包括分散在溶剂中的聚偏二氟乙烯(PVDF)和聚(偏氟乙烯-六氟丙烯)(PVdF-HFP)共聚物，以使该溶液具有在300cP至1500cP之间的聚合物粘度；和
该多个工艺参数包括：
在20kV和50kV之间的电压；
在3ml/h和12ml/h之间的馈送率；和
在100mm和150mm之间的旋转高度。
2.根据权利要求1所述的方法，其中共聚物中使用的PVDF和PVdF-HFP具有在1:1和5:1之间的重量比。
3.根据权利要求1所述的方法，其中溶剂包括二甲基甲酰胺(DMF)和丙酮。
4.根据权利要求3所述的方法，其中溶液中使用的DMF和丙酮具有在1:2和8:2之间的重量比。
5.根据权利要求1所述的方法，其中共聚物的重量是共聚物和溶剂的总重量的5％至25％。
6.根据权利要求1所述的方法，其中多个工艺参数还包括：
在20％和50％之间的环境湿度。
7.根据权利要求1所述的方法，其中衬底由聚丙烯(PP)或聚乙烯(PE)组成，或者为三层PP/PE/PP电解分离膜。
8.根据权利要求1所述的方法，进一步包括：
通过静电纺丝工艺在衬底的第二表面上沉积第二静电纺丝层，第二表面与第一表面相对。
9.一种通过前述权利要求中的任一项的方法形成的柔性多孔膜。
10.一种柔性电池，其包括：
包括权利要求9的柔性多孔膜的固体电解质，其中柔性多孔膜进一步用液体电解质浸透。
11.根据权利要求10所述的柔性电池，其中液体电解质是LiPF6、LiClO4、(C2H5)4AN、H2O、H2SO4、NaOH、NaCl或其组合。
12.根据权利要求10所述的柔性电池，进一步包括：
耦合到固体电解质的一个表面的阳极；和
耦合到固体电解质的另一个表面的阴极，所述另一个表面与所述一个表面相对。
13.根据权利要求12所述的柔性电池，进一步包括：
耦合到阳极的第一集电器；和
耦合到阴极的第二集电器。
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