CN106638007A - 一种基于静电纺丝技术的陶瓷隔膜及其制备方法 - Google Patents
一种基于静电纺丝技术的陶瓷隔膜及其制备方法 Download PDFInfo
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- CN106638007A CN106638007A CN201611196385.9A CN201611196385A CN106638007A CN 106638007 A CN106638007 A CN 106638007A CN 201611196385 A CN201611196385 A CN 201611196385A CN 106638007 A CN106638007 A CN 106638007A
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
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- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
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- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明公开了一种基于静电纺丝技术的陶瓷隔膜及其制备方法,首先采用纺丝纳米纤维层作为基膜,然后将陶瓷浆料或者陶瓷前驱体溶液涂覆/铸涂在基膜上,最终制备得到产品。本发明得到的陶瓷隔膜孔隙率高,厚度薄、离子通透性好的同时,引入陶瓷颗粒,极大地减少了隔膜的热收缩,提高了隔膜的耐高温性能。
Description
技术领域
本发明属于锂离子电池技术领域,特别涉及一种陶瓷隔膜及其制备方法。
背景技术
隔膜是锂离子电池中必不可少的重要组成部分,一方面隔离正、负极极片以避免之间发生接触短路,另一方面是允许锂离子在电池充放电的过程中自由的穿梭以满足电能的储存和释放。锂电池隔膜优劣对锂电池性能影响很大,如电池内阻、放电容量、循环寿命以及电池安全性能的好坏。一般情况下,隔膜的厚度越薄、孔隙率越高,电池的内阻越小,高倍率放电性能也就越好。另外,隔膜的闭孔温度和破膜温度对于电池的安全性能影响很大,一般会选择闭孔温度低,破膜温度高的隔膜,这样的电池的安全性能更好,且电池的应用范围更广。
电池隔膜一般是用聚乙烯(PE)、聚丙烯(PP)来制备,分为单层PE、PP膜,3层PP、PE膜。电池隔膜的制备方法分为干法和湿法两类,干法是将聚烯烃树脂熔融、挤压、吹膜制成结晶性聚合物薄膜,经过结晶化处理、退火后,得到高度取向的多层结构,在高温下进一步拉伸,将结晶界面进行剥离,形成多孔结构,可以增加薄膜的孔径。湿法又称相分离法或热致相分离法,将液态烃或一些小分子物质与聚烯烃树脂混合,加热熔融后,形成均匀的混合物,然后降温进行相分离,压制得膜片,再将膜片加热至接近熔点温度,进行双向拉伸使分子链取向,最后保温一定时间,用易挥发物质洗脱残留的溶剂,可制备出相互贯通的微孔膜。聚乙烯、聚丙烯隔膜的主要缺点为表面能低,保液率低。同时聚乙烯、聚丙烯隔膜在85-100℃即会发生收缩,110℃即可发生显著变形,稍有不慎即会造成电池的内短路而引发安全事故。
动力电池的隔膜为了提高动力电池的安全性,目前大多是在微孔膜的一面或两面涂上陶瓷浆料而制成的,陶瓷浆料的主要作用是防止微孔膜在高温下收缩,起到骨架支撑作用。但是,用这种方式制作电池隔膜在较高的温度下,微孔膜还是会有收缩现象,为了防止这种现象的发生,人们不得不加上一些温控电路来解决这个问题,即当检测到电池温度高于预定值时,自动切断电池的充电或放电电路,以控制电池的温度继续上升,这不仅增加了电池使用过程中的成本,而且,当温控电路出现问题时,会出现不可想象的电池爆炸问题。
目前市场上用的陶瓷隔膜多为氧化铝附着在基膜上,用以增强基膜的耐高温性能。为了增强陶瓷材料和基膜的附着效果,一般会在陶瓷浆料中加入一些有机粘结剂,如聚氨酯、胶黏剂,这些有机粘结剂需要借助有机溶剂进行分散,且在涂覆烘干工艺中会挥发,同时还会增加生产污染、增加了陶瓷隔膜的成本,也不利于陶瓷隔膜在锂离子电池中普及应用。
随着三元电池的推广以及磷酸铁锂电池能量密度的提升需求,陶瓷隔膜代替普通隔膜是未来高能量和高功率的大电池的必然选择,也是市场和科技的综合需要,掌握陶瓷浆料制备技术、隔膜涂覆技术对于提升自主研发锂离子电池的整体竞争力、对完善产业链结构具有重要的作用。
CN104332575A、CN105845870A、CN103311485A等公开了部分隔膜的制备方法,这些方法尽管提高了传统隔膜耐高温性能差的特点,但是其是在已有隔膜基础上涂覆陶瓷层,未提高产品的孔隙率和保液率,同时一定程度上增大了隔膜厚度。已公开的CN102557628A,CN102242464A等专利申请采用静电纺丝纤维和纳米陶瓷相复合的工艺形式制备出陶瓷隔膜,以提高隔膜的耐热性能。但是其实现形式是将陶瓷浆料或者陶瓷前驱体溶液直接加入静电纺料液中去,通过静电纺丝工艺制备出复合隔膜。但是采用该静电纺丝工艺制备出的纳米纤维隔膜,纤维为无序堆叠结构,力学性能差,隔膜孔径不均,成品率低。
发明内容
为了克服上述技术问题,本发明提供了一种高孔隙率、高保液率、低厚度、高绝缘、耐高温的陶瓷隔膜的制备方法,采用该方法制备的隔膜,能有效提高动力电池的整体性能和安全性。
本发明的技术方案如下:
一种基于静电纺丝技术的陶瓷隔膜的制备方法,包括如下步骤:
1)使用高分子材料配置成5-20wt%的纺丝液,使用静电纺丝技术制备成纤维直径为50-1000nm的纳米纤维膜;
2)将陶瓷粒子、粘结剂和溶剂混合均匀制成浆料,并将浆料均匀涂覆或铸涂在步骤1)的纳米纤维膜表面,优选陶瓷粒子含量为1-60wt%,粘结剂含量1-55wt%,剩余为溶剂;
3)通过烘干、紫外辐照工艺使陶瓷粒子粘结在一起,制得锂电池隔膜。
进一步地,所述高分子材料为尼龙6、聚丙烯腈、聚偏氟乙烯、聚己内酯、聚乳酸、聚乙烯吡络烷酮、聚对苯二甲酸乙二醇酯、聚氨酯、聚酰亚胺、乙烯/乙烯醇共聚物、聚羟基乙酸、聚环氧乙烷和聚乙烯醇中的一种或者多种。
进一步地,所述陶瓷粒子包括硅、钼、锆、钛、铝、硼元素的氧化物、氮化物、硼化物和/或碳化物。
进一步地,所述陶瓷粒子通过偶联处理,提高陶瓷粒子的粘结性,偶联剂采用有机硅乳液,陶瓷粒子与有机硅乳液的重量比为1:1-10。
进一步地,所述粘结剂包括聚乙烯醇、聚乙烯醇缩丁醛和/或聚偏氟乙烯。
进一步地,所述溶剂为甲醇、乙醇、水和/或N-甲基吡咯烷酮。
本发明还提供了另外一种基于静电纺丝技术的陶瓷隔膜的制备方法,包括如下步骤:
1)使用高分子材料配置成5-20wt%的纺丝液,使用静电纺丝技术制备成纤维直径为50-1000nm的纳米纤维膜;
2)配置陶瓷前驱体溶液,并将前驱体溶液均匀涂覆或铸涂在步骤1)的纳米纤维膜表面;
3)通过酸碱催化水解、高温降解工艺使陶瓷前驱体水解或者降解,在纳米纤维膜中形成陶瓷层,制得锂电池隔膜。
进一步地,所述高分子材料为尼龙6、聚丙烯腈、聚偏氟乙烯、聚己内酯、聚乳酸、聚乙烯吡络烷酮、聚对苯二甲酸乙二醇酯、聚氨酯、聚酰亚胺、乙烯/乙烯醇共聚物、聚羟基乙酸、聚环氧乙烷和聚乙烯醇中的一种或者多种。
进一步地,所述陶瓷前驱体溶液包括正硅酸乙酯、聚碳硅烷、硼吖嗪的聚硼硅氮烷和聚氮硅烷的单一原料的前驱体溶液或混合前驱体溶液,例如氧氯化锆、硼酸、蔗糖和柠檬酸配制成的混合硼化锆前驱体溶液,其中n(Zr):n(c)=1:4-6.5,硼酸过量本发明还提供了利用上述两种方法制备得到的陶瓷隔膜,陶瓷隔膜孔隙率大于70%,在130℃条件下处理1h后,横向收缩小于3%,纵向收缩小于5%。
本发明使用静电纺丝技术制备基膜,创造性的提出了利用陶瓷浆料或者前驱体溶液涂覆或铸涂基膜,保证了纳米纤维隔膜孔隙率高,厚度薄、离子通透性好的同时,引入陶瓷颗粒,极大地减少了隔膜的热收缩,提高了隔膜的耐高温性能。同时陶瓷浆料/前驱体溶液在毛细作用下会更多的填充在纳米纤维膜的大孔径位置,弥补了纳米纤维隔膜,纤维为无序堆叠结构,隔膜孔径不均,成品率低的缺陷。
具体实施方式
下面结合具体实施例对本发明做进一步说明。
实施例1
一种基于静电纺丝技术的陶瓷隔膜,采用如下方法制备:
1)配置12wt%浓度的PVDF溶液,使用静电纺丝工艺制备出纳米纤维直径为150-220nm,厚度为18μm的纳米纤维膜,纺丝条件为:温度25℃,湿度40%,纺丝电压22kV,针板距离为18cm,料液流速为1mL/h;
2)将平均粒径0.1~3μm的介孔Al2O3陶瓷粒子表面进行偶联处理,具体方法是:将陶瓷粉体与浓度为2wt%的有机硅乳液进行混合,陶瓷粉体与有机硅乳液的比例为1:5(重量比),混合均匀后,将体系在150℃烘干20小时;
3)将15wt%的Al2O3陶瓷粒子、2.5wt%的聚乙烯醇缩丁醛粘结剂和82.5wt%的溶剂混合均匀制成浆料;
4)将浆料均匀地通过涂布设备涂敷到隔膜上,形成4μm厚度的隔膜层。将涂布后的隔膜通过烘箱,在85℃温度烘干2小时,形成涂覆好的隔膜。将隔膜收卷,得到电池隔膜。
所制备出的陶瓷隔膜,厚度为21μm,孔径大小为0.02-0.09μm,孔隙率为75%,在130℃条件下处理1h,横向收缩为1.3%,纵向收缩为2%,产品性能稳定,可以在很大程度上满足动力电池的要求。
实施例2
一种基于静电纺丝技术的陶瓷隔膜,采用如下方法制备:
1)配置18wt%浓度的聚乙烯吡咯烷酮溶液,使用静电纺丝工艺制备出纳米纤维直径为150-220nm,厚度为18μm的纳米纤维膜,纺丝条件为:温度25℃,湿度40%,纺丝电压22kV,针板距离为18cm,料液流速为1mL/h;
2)将平均粒径0.1~3μm的二氧化硅粒子和氮化钛粒子表面进行偶联处理,二氧化硅粒子和氮化钛粒子的重量比为3:1,具体方法是:将二氧化硅粒子和氮化钛粒子组成的陶瓷粉体与浓度为5wt%的有机硅乳液进行混合,陶瓷粉体与有机硅乳液的比例为1:8(重量比),混合均匀后,将体系在150℃烘干20小时;
3)将30wt%的上述陶瓷粒子、12.5wt%的聚乙烯醇缩丁醛粘结剂和57.5wt%的溶剂混合均匀制成浆料;
4)将浆料均匀地通过涂布设备涂敷到隔膜上,形成4μm厚度的隔膜层。将涂布后的隔膜通过烘箱,在60℃温度烘干2小时,形成涂覆好的隔膜。将隔膜收卷,得到电池隔膜。
所制备出的陶瓷隔膜,厚度为21μm,孔径大小为0.02-0.09μm,孔隙率为83%,在130℃条件下处理1h,横向收缩为1.1%,纵向收缩为1.3%,产品性能稳定,可以在很大程度上满足动力电池的要求。
实施例3
一种基于静电纺丝技术的陶瓷隔膜,采用如下方法制备:
1)配置18wt%浓度的PVDF溶液,使用静电纺丝工艺制备出纳米纤维直径为150-220nm,厚度为18μm的纳米纤维膜,纺丝条件为:温度25℃,湿度40%,纺丝电压22KV,针板距离为18cm,料液流速为1mL/h;
2)准确称量正硅酸乙酯,将其溶解在乙醇中,配制出3wt%的乙醇溶液,并加入正硅酸乙酯体积分数30%体积的氨水,控制氨水pH为11,搅拌12h,配制出前驱体溶液;
3)将前驱体溶液均匀地通过涂布设备涂敷到隔膜上,形成4μm厚度的隔膜层。将涂布后的隔膜通过烘箱,在85℃温度烘干2小时,得到电池隔膜。
所制备出的陶瓷隔膜,厚度为21μm,孔径大小为0.02-0.09μm,孔隙率为88%,在130℃条件下处理1h,横向收缩小于1.4%,纵向收缩小于1.1%,产品性能稳定,可以在很大程度上满足动力电池的要求。
实施例4
一种基于静电纺丝技术的陶瓷隔膜,采用如下方法制备:
1)配置18wt%浓度的聚酰亚胺溶液,使用静电纺丝工艺制备出纳米纤维直径为150-220nm,厚度为18μm的纳米纤维膜,纺丝条件为:温度25℃,湿度40%,纺丝电压22KV,针板距离为18cm,料液流速为1mL/h;
2)准确称量氧氯化锆、硼酸、蔗糖和柠檬酸,配制成的混合硼化锆前驱体溶液,其中n(Zr):n(c)=1:5.5,硼酸过量;
3)将前驱体溶液均匀地通过涂布设备涂敷到隔膜上,形成4μm厚度的隔膜层。将涂布后的隔膜通过烘箱,在60℃温度烘干2小时,得到电池隔膜。
所制备出的陶瓷隔膜,厚度为21μm,孔径大小为0.02-0.09μm,孔隙率为95%,在130℃条件下处理1h,横向收缩0.8%,纵向收缩0.6%,产品性能稳定,可以在很大程度上满足动力电池的要求。
对比例1
市售PE隔膜A其厚度为25微米,孔径大小为0.03-0.24μm,孔隙率40%,在130℃条件下处理1h,横向收缩14%,纵向收缩小于21%,产品孔隙率低,耐热性能差,无法满足动力电池要求。
对比例2
一种陶瓷隔膜,采用如下方法制备:
1)使用市售PE隔膜作为基膜;
2)将平均粒径0.1~3μm的介孔Al2O3陶瓷粒子表面进行偶联处理,具体方法是:将陶瓷粉体与0.1~5%浓度的有机硅乳液进行混合,陶瓷粉体与有机硅乳液的比例为1:1~10(重量比),混合均匀后,将体系在100~200℃烘干2~30小时;
3)将Al2O3陶瓷粒子、聚乙烯穿缩丁醛粘结剂和溶剂混合均匀制成浆料,控制Al2O3陶瓷粒子质量分数为15wt%,粘结剂聚乙烯醇缩丁醛浓度为2.5wt%;
4)将浆料均匀地通过涂布设备涂敷到PE隔膜上,在60℃温度烘干2小时,形成涂覆好的隔膜。将隔膜收卷,得到电池隔膜。
所制备出的的陶瓷隔膜,厚度为27μm,孔径大小为0.02-0.13μm,孔隙率为41%,在130℃条件下处理1h,横向收缩率为9%,纵向收缩为9.7%,产品耐热性能相对稳定,可以在一定程度上满足动力电池的要求。但是该隔膜孔隙率、离子通透率、耐热性、隔膜厚度等关键性能参数均劣于本专利产品。
对比例3
一种陶瓷隔膜,采用如下方法制备:
1)准确称量聚偏氟乙烯聚合物,加入到n,n-二甲基甲酰胺溶剂,45-50℃搅拌6h,制备出14wt%纺丝原液;
2)将陶瓷材料加入到等质量n,n-二甲基甲酰胺溶剂中,超声分散处理后将其加入到上述聚合物溶液中,室温下以行星式球磨机研磨得到复合纺丝溶液;其中,复合纺丝溶液中的陶瓷材料的质量为聚合物-陶瓷总质量的20%;
3)用静电纺丝工艺制备出厚度为22μm的纳米纤维膜,纺丝条件为:温度25℃,湿度40%,纺丝电压22KV,针板距离为18cm,料液流速为1mL/h;
4)将隔膜收卷,60℃烘干2h,得到对比例3电池隔膜。
所制备出的的陶瓷隔膜,厚度为21μm,孔径大小为0.03-1.23μm,孔隙率为89%,在130℃条件下处理1h,横向收缩率为2.2%,纵向收缩为4.7%。产品耐热性能优良,孔隙率高于本发明产品,但是生成的纳米纤维隔膜为无序堆叠结构,力学性能差,隔膜孔径不均,成品率低;当隔膜出现大孔径时,极易引起电池内部微短路,起火,甚至酿成事故。
Claims (10)
1.一种基于静电纺丝技术的陶瓷隔膜的制备方法,其特征在于,包括如下步骤:
1)使用高分子材料配置成浓度为5-20wt%的纺丝液,使用静电纺丝技术制备成纤维直径为50-1000nm的纳米纤维膜;
2)将陶瓷粒子、粘结剂和溶剂混合均匀制成浆料,并将浆料均匀涂覆或铸涂在步骤1)的纳米纤维膜表面,优选陶瓷粒子含量为1-60wt%,粘结剂含量1-55wt%,剩余为溶剂;
3)通过烘干、紫外辐照工艺使陶瓷粒子粘结在一起,制得锂电池隔膜。
2.根据权利要求1所述的制备方法,其特征在于,所述高分子材料为尼龙6、聚丙烯腈、聚偏氟乙烯、聚己内酯、聚乳酸、聚乙烯吡络烷酮、聚对苯二甲酸乙二醇酯、聚氨酯、聚酰亚胺、乙烯/乙烯醇共聚物、聚羟基乙酸、聚环氧乙烷和聚乙烯醇中的一种或者多种。
3.根据权利要求1所述的制备方法,其特征在于,所述陶瓷粒子包括硅、钼、锆、钛、铝、硼元素的氧化物、氮化物、硼化物和/或碳化物。
4.根据权利要求3所述的制备方法,其特征在于,所述陶瓷粒子通过偶联处理,提高陶瓷粒子的粘结性,偶联剂采用有机硅乳液,陶瓷粒子与有机硅乳液的重量比为1:1-10。
5.根据权利要求1所述的制备方法,其特征在于,所述粘结剂包括聚乙烯醇、聚乙烯醇缩丁醛和/或聚偏氟乙烯。
6.根据权利要求1所述的制备方法,其特征在于,所述溶剂为甲醇、乙醇、水和/或N-甲基吡咯烷酮。
7.一种基于静电纺丝技术的陶瓷隔膜的制备方法,包括如下步骤:
1)使用高分子材料配置成浓度为5-20wt%的纺丝液,使用静电纺丝技术制备成纤维直径为50-1000nm的纳米纤维膜;
2)配置陶瓷前驱体溶液,并将前驱体溶液均匀涂覆或铸涂在步骤1)的纳米纤维膜表面;
3)通过酸碱催化水解、高温降解工艺使陶瓷前驱体水解或者降解,在纳米纤维膜中形成陶瓷层,制得锂电池隔膜。
8.根据权利要求7所述的制备方法,其特征在于,所述高分子材料为尼龙6、聚丙烯腈、聚偏氟乙烯、聚己内酯、聚乳酸、聚乙烯吡络烷酮、聚对苯二甲酸乙二醇酯、聚氨酯、聚酰亚胺、乙烯/乙烯醇共聚物、聚羟基乙酸、聚环氧乙烷和聚乙烯醇中的一种或者多种。
9.根据权利要求7所述的制备方法,其特征在于,所述陶瓷前驱体溶液包括正硅酸乙酯、聚碳硅烷、硼吖嗪的聚硼硅氮烷和聚氮硅烷的单一原料的前驱体溶液或混合前驱体溶液,例如氧氯化锆、硼酸、蔗糖和柠檬酸配制成的混合硼化锆前驱体溶液,其中n(Zr):n(c)=1:4-6.5,硼酸过量。
10.本发明还提供了利用上述两种方法制备得到的陶瓷隔膜,陶瓷隔膜孔隙率大于70%,在130℃条件下处理1h后,横向收缩小于3%,纵向收缩小于5%。
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Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102832367A (zh) * | 2012-08-31 | 2012-12-19 | 浙江大东南包装股份有限公司 | 一种锂离子二次电池隔膜及其制备方法 |
CN103311485A (zh) * | 2013-05-06 | 2013-09-18 | 北京鼎能开源电池科技股份有限公司 | 锂离子电池隔膜表面陶瓷化的方法 |
CN103515561A (zh) * | 2012-06-29 | 2014-01-15 | 安炬科技股份有限公司 | 电化学装置隔离膜及其制备方法 |
CN104064712A (zh) * | 2014-07-10 | 2014-09-24 | 厦门大学 | 一种锂离子电池陶瓷隔膜粘结剂的选择方法 |
CN105826508A (zh) * | 2016-05-27 | 2016-08-03 | 北京师范大学 | 压电陶瓷复合隔膜、其制备方法及锂离子电池 |
-
2016
- 2016-12-22 CN CN201611196385.9A patent/CN106638007A/zh active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103515561A (zh) * | 2012-06-29 | 2014-01-15 | 安炬科技股份有限公司 | 电化学装置隔离膜及其制备方法 |
CN102832367A (zh) * | 2012-08-31 | 2012-12-19 | 浙江大东南包装股份有限公司 | 一种锂离子二次电池隔膜及其制备方法 |
CN103311485A (zh) * | 2013-05-06 | 2013-09-18 | 北京鼎能开源电池科技股份有限公司 | 锂离子电池隔膜表面陶瓷化的方法 |
CN104064712A (zh) * | 2014-07-10 | 2014-09-24 | 厦门大学 | 一种锂离子电池陶瓷隔膜粘结剂的选择方法 |
CN105826508A (zh) * | 2016-05-27 | 2016-08-03 | 北京师范大学 | 压电陶瓷复合隔膜、其制备方法及锂离子电池 |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109449353A (zh) * | 2018-10-19 | 2019-03-08 | 刘建宏 | 一种新型锂电池隔膜 |
CN109825900A (zh) * | 2019-01-23 | 2019-05-31 | 中国人民解放军国防科技大学 | 一种bcn纳米陶瓷纤维的制备方法 |
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CN110042504A (zh) * | 2019-03-14 | 2019-07-23 | 国装新材料技术(江苏)有限公司 | 具有凝胶纺丝功能的环糊精复合陶瓷前驱体及制备方法 |
CN110061175A (zh) * | 2019-04-26 | 2019-07-26 | 东莞东阳光科研发有限公司 | 锂电池、锂电池隔膜及其制备方法 |
CN110224098A (zh) * | 2019-06-10 | 2019-09-10 | 合肥众禾动力新能源科技有限公司 | 一种锂离子电池卷芯 |
CN110518177A (zh) * | 2019-07-15 | 2019-11-29 | 青岛大学 | SiO2/PVDF-HFP复合纤维膜及其制备方法和应用 |
CN110518177B (zh) * | 2019-07-15 | 2022-05-06 | 青岛大学 | SiO2/PVDF-HFP复合纤维膜及其制备方法和应用 |
CN112143228A (zh) * | 2020-09-27 | 2020-12-29 | 江西新科环保股份有限公司 | 碳化硅陶瓷平板膜 |
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Application publication date: 20170510 |