CN104183867B - 一种单离子导体纳米颗粒增强锂电池隔膜或聚合物电解质的制备方法和应用 - Google Patents
一种单离子导体纳米颗粒增强锂电池隔膜或聚合物电解质的制备方法和应用 Download PDFInfo
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Abstract
本发明属于锂电池隔膜技术领域,尤其涉及一种纳米单离子导体涂覆锂电池隔膜及其制备方法。本发明所述的锂电池隔膜是以聚合物多孔膜或无纺布为基材,采用单离子导体纳米颗粒和聚合物对基材进行表面修饰得到的。本发明所制备的高性能低温锂电池隔膜厚度为5µm‑100µm,透气度为1 s‑1000 s/100 cc,孔隙率为30%‑85%,孔径范围为0.02µm‑8µm,电解液吸收率为100%‑800%。本发明所提供的涂覆隔膜低温性能优良,离子迁移数和离子电导率高、倍率性能和长循环性能好并且改善其与正负材料之间的界面稳定性。同时,本发明所提供的制备工艺简单易行,生产成本低廉,易于大规模生产。
Description
技术领域
本发明涉及一种单离子导体纳米颗粒增强的锂电池聚合物电解质或者隔膜;本发明还涉及上述的单离子导体纳米颗粒涂覆的锂电池聚合物电解质或隔膜的制备方法。
背景技术
聚合物电解质和隔膜是位于锂电池正负极之间,其作用非常的重要,起到隔离正极和负极,防止电池内部短路,同时在电池充放电过程中能够使锂离子快速传输等作用,其是锂离子电池的重要组成部分之一。聚合物电解质的性能决定了电池的安全性能和内阻,直接影响电池的充放电效率、容量和循环使用寿命等特性。用做锂离子电池隔膜的材料,要具备好的机械强度、耐电解液腐蚀能力、低的电阻等特性。性能优异的聚合物电解质和隔膜对提高电池的综合性能具有重要的作用。目前,市场上的锂离子电池的电解质体系包括隔膜和电解液,而隔膜主要是聚烯烃微孔膜,包括聚乙烯、聚丙烯、以及聚乙烯/聚丙烯复合膜。聚烯烃微孔膜具有优良的纵向拉伸强度,良好的电化学稳定性。但也存在许多缺点:其对电解液的浸润性不好,离子电导率低,热收缩性能差等问题。
由于目前市场上的隔膜都单纯的起到简单的隔离作用,在相同的孔径下,其对锂离子电导率的提高没有任何的帮助。然而据我们所知,截至目前并没有把单离子导体纳米颗粒涂覆到锂电池隔膜或电解质的方法来提高锂电池的电化学性能的报道。鉴于此,本发明将单离子导体纳米颗粒和聚合物复合浆料在无纺膜上进行刮涂或浸涂,成功制备了单离子导体纳米颗粒增强的锂电池电解质体系,并将其应用于锂电池隔膜等领域。
发明内容
本发明的目的在于提供了一种单离子导体纳米颗粒增强的锂电池隔膜或者聚合物电解质,提高现有电池电解质的各项性能。
本发明的另一目的在于提供制备一种单离子导体纳米颗粒涂覆锂电池聚合物电解质和隔膜的方法。
为实现上述目的,本发明提供的一种单离子导体纳米颗粒涂布锂电池隔膜或电解质为单离子导体纳米颗粒和聚合物混合浆料涂覆到基材而制备的高性能锂电池电解质体系,离子导电率高于10-3 S/cm,孔径为500 nm - 2000 nm,膜厚度为5μm - 100μm,膜透气率为1 s- 1000 s/100 cc,纵、横向拉伸强度20 - 200 MPa,90℃下收缩率< 2%。所述基材包括聚烯烃微孔膜,聚酯(PET)无纺布,尼龙无纺布,芳纶无纺布,聚氨酯无纺布,芳砜纶无纺布,纤维素无纺膜和聚偏氟乙烯(PVDF)无纺布中的一种或多种复合。所述单离子导体纳米颗粒和聚合物混合浆料为单离子导体纳米颗粒和聚合物按一定的比例配置,其中单离子导体纳米颗粒质量与聚合物质量比为0.1 :1~ 5:1。所述聚合物为聚乙烯醇、聚醋酸乙烯酯、聚偏氟乙烯(PVDF) 、聚丙烯腈(PAN) 、聚甲基丙烯酸甲酯(PMMA) 、聚氧化乙烯(PEO)、聚乙烯基缩丁醛(PVB)、聚三氟氯乙烯(PCTFE)、聚苯乙烯和聚偏二氟乙烯-六氟丙烯(PVDF-HFP)中的一种或多种。所述单离子导体纳米颗粒包括单离子导体的一种或多种,单离子导体为聚合物硼酸酯锂盐,其化学结构如通式1所示:
通式1
其中X1,X2,X3,X4为:
,,,,,,或;
R为C1-C5烷基、C1-C5氟代烷基的一种。
Y为:直链或带支链的烷基,直链或带支链的氟代烷基,芳基,氟代芳基的至少一种。
具体结构式包括如下:
,,,,,,,,,,
。
为实现上述目的,本发明所采取的制备方法是对单离子导体纳米颗粒和聚合物混合浆料进行刮涂或者浸涂等工艺,实验步骤如下:
a. 制备单离子导体纳米颗粒和聚合物混合浆料:将一种或多种上述的聚合物,一种或多种上述的单离子导体和溶剂按一定浓度配比进行研磨成单离子导体纳米颗粒和聚合物混合浆料或溶液,真空脱除气泡,静置备用;
b. 对单离子导体纳米颗粒和聚合物混合浆料或溶液进行刮涂或浸涂:将步骤a制备的混合浆料或溶液注入刮槽,调节涂布的厚度参数、涂布拉伸张力和涂布速度,在一定的温度下烘干收卷。
在所述的一种单离子导体纳米颗粒增强的锂电池聚合物电解质或隔膜的制备方法中,溶液的浓度为5 % -25 %,所用溶剂包括乙酸乙酯、甲醇、乙醇、丙三醇、丙酮、甲酸、乙酸、碳酸二甲酯、碳酸二乙酯、碳酸甲乙酯、碳酸甲丙酯、碳酸乙丙酯、γ-丁内酯、二甲基亚砜、环丁砜、二甲基砜、四氢呋喃、N-甲基吡咯烷酮、N、N-二甲基甲酰胺、N、N-二甲基乙酰胺中的一种或多种。所述的刮刀厚度为2μm -150μm,拉伸张力为2 MPa – 50 MPa,涂布速度为500 mm/min – 5000 mm/min。干燥温度为50 ℃ - 130 ℃。
一种单离子导体纳米颗粒增强的锂电池聚合物电解质或隔膜应用于锂金属电池、锂离子动力电池和储能电池。
附图说明
图1为本发明实施例1制备的纤维素基复合高性能锂电池隔膜或聚合物电解质表面的扫描电镜照片 。
图2为实施例1、实施例2制备高性能锂电池隔膜和聚丙烯隔膜后的钴酸锂/石墨全电池倍率曲线图。
图3为实施例1、实施例2制备高性能锂电池隔膜和聚丙烯隔膜的钴酸锂/石墨全电池长循环曲线图。
图4为单离子导体纳米颗粒和实施例1制备的单离子导体纳米颗粒涂覆锂电池隔膜的XRD对照图。
具体实施方式
以上是对本发明的一般性描述,下面我们将通过具体实施例对本发明的权利要求作进一步的解释。
实施例1
称取100 g单离子导体(聚合季戊四醇硼酸酯锂盐)、50 g聚偏二氟乙烯溶解于2000 g N、N-二甲基乙酰胺中,机械研磨3 h后,得到均匀的纳米单离子导体/聚偏二氟乙烯混合浆料。取500 g 混合浆料倒入涂槽中,使用纤维素无纺布为基材,将浆料涂布到纤维素无纺布基材上,刮刀厚度为50μm,拉伸张力为15 MPa,涂布速度为1500 mm/min,干燥温度为80 ℃。得到厚度为30 μm的 单离子导体纳米颗粒增强的电池隔膜或电解质。
实施例2
称取100 g单离子导体(聚丁四酸硼酸酯锂盐)、80 g聚丙烯腈溶解于200 g N、N-二甲基乙酰胺和800 g丙酮中,机械研磨3 h后,得到均匀的纳米单离子导体/聚丙烯腈混合浆料。取500 g 混合浆料倒入涂槽中,使用聚丙烯无纺布为基材,将浆料涂布到聚丙烯基材上,刮刀厚度为35μm,拉伸张力为30 MPa,涂布速度为2000 mm/min,干燥温度为80 ℃。得到厚度为25 μm的单离子导体纳米颗粒增强的电池隔膜或者电解质。
实施例3
称取50 g单离子导体(聚酒石酸硼酸酯锂盐)、50 g 聚偏二氟乙烯-六氟丙烯溶解于500 g N、N-二甲基甲酰胺和500 g N-甲基吡咯烷酮中,机械研磨3 h后,得到均匀的纳米单离子导体/聚偏二氟乙烯-六氟丙烯混合浆料。取500 g 混合浆料倒入涂槽中,使用聚酯无纺布为基材,将浆料涂布到聚酯无纺布基材上,刮刀厚度为40μm,拉伸张力为10 MPa,涂布速度为1800 mm/min,干燥温度为120 ℃。得到厚度为30 μm的单离子导体纳米颗粒涂布的电池隔膜或者聚合物电解质。本发明不仅局限于以上实施方式,可以根据物料配比、刮刀厚度、涂布速度和干燥温度等来制备满足锂电池隔膜所需要的产品型号和规格。本领域的科研人员还可以做出各种改变和变形,在本专利主旨的前提下,均在本专利的范围内。
对比例:采用商业化的聚丙烯隔膜作为对比,以进一步阐明本专利中所述的单离子导体纳米颗粒涂布的电池隔膜或者电解质的优点。
对实施例1-3所制得的纳米单离子导体和聚合物混合浆料涂覆到无纺膜和对比例中的聚丙烯隔膜进行离子电导率、低温离子电导率、孔隙率、透气性、电解液吸收率、表面形貌和电池性能的表征,结果如表1、图1、图2和图3所示。不难得出:本专利所提供的纳米单离子导体涂布的电池隔膜具有很高的离子电导率、以及低温离子电导率也比商业PP隔膜好很多、比孔隙率高、电解液吸收多、充放电曲线稳定和循环稳定性好等优点,符合高性能锂电池隔膜的要求。
表1
Claims (6)
1.一种单离子导体纳米颗粒增强的锂电池隔膜,其特征在于:所述锂电池隔膜为单离子导体纳米颗粒和聚合物混合浆料涂覆到基材而制备的高性能锂电池隔膜,单离子导体纳米颗粒的结构如下所示:,,,聚合物为聚丙烯腈和聚苯乙烯,所述单离子导体纳米颗粒增强的锂电池隔膜的制备包括如下步骤:a. 制备单离子导体纳米颗粒和聚合物混合浆料:将一种或多种上述聚合物、一种或多种上述单离子导体和适当溶剂按一定浓度配比进行研磨成单离子导体纳米颗粒和聚合物混合浆料,真空脱除气泡,静置备用;b. 对单离子导体纳米颗粒和聚合物混合浆料进行刮涂:将步骤a制备的混合浆料注入刮槽,调节涂布的厚度参数、涂布拉伸张力和涂布速度,在一定的温度下烘干收卷。
2.根据权利要求1所述的一种单离子导体纳米颗粒增强的锂电池隔膜,其特征在于:离子导电率高于10-3 S/cm,孔径为500 nm - 2000 nm,膜厚度为5 μm - 100 μm,膜透气率为1s - 1000s/100cc,纵、横向拉伸强度为20 ~ 200 MPa,90℃下收缩率< 2%。
3.根据权利要求1所述的一种单离子导体纳米颗粒增强的锂电池隔膜,其特征在于:所述的基材为聚烯烃微孔膜、聚酯(PET)无纺布、尼龙无纺布、芳纶无纺布、芳砜纶无纺布、聚氨酯无纺布、纤维素无纺膜和聚偏氟乙烯(PVDF)无纺布中的一种或多种。
4.根据权利要求1所述的一种单离子导体纳米颗粒增强的锂电池隔膜,其特征在于:浆料的浓度为5 % - 25 %,所用适当的溶剂为乙酸乙酯、甲醇、乙醇、丙三醇、丙酮、甲酸、乙酸、碳酸二甲酯、碳酸二乙酯、碳酸甲乙酯、碳酸甲丙酯、碳酸乙丙酯、γ-丁内酯、二甲基亚砜、环丁砜、二甲基砜、四氢呋喃、N-甲基吡咯烷酮、N、N-二甲基甲酰胺、N、N-二甲基乙酰胺中的一种或多种。
5.根据权利要求1所述的一种单离子导体纳米颗粒增强的锂电池隔膜,其特征在于:所述拉伸张力为2 MPa - 50 MPa,涂布速度为500 mm/min - 5000 mm/min,干燥温度为50 ℃- 130 ℃。
6.权利要求1所述的一种单离子导体纳米颗粒增强的锂电池隔膜应用于锂金属电池、锂离子动力电池和储能电池。
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